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By W. Mckewan, W. M. Fassell

The oxidation rates of copper have been determined at temperatures from 600" to 900°C in oxygen from 14.7 to 400 psi total oxygen pressure. The oxidation rate of copper is unchanged by oxygen pressures within the range studied. The observed data extend Feit-knecht's conclusion concerning the pressure independence of copper from atmospheric pressure to 400 psi. All samples studied in the above-mentioned temperature and pressure range have both Cu2O and CuO present in the oxide film. NUMEROUS papers have been published on the oxidation of copper, some of which have noted the effect of oxygen pressure on the oxidation rate of copper. It must be noted, however, that no data on the oxidation rates of copper at pressure in excess of 1 atm have been reported in the literature. (Le Chatelier¹ reported that a black oxide of silver was formed at 300°C and 15 atm pressure.) This is likewise true for the other metals. This investigation was initiated to obtain experimental oxidation rate constants for pure metals at elevated temperatures and high oxygen pressure. Copper was selected as the first metal since probably more reliable data are available on its oxidation rates and related physical and chemical properties than for any other metal or alloy. As a general summary, the following conclusions appear well established for the oxidation of copper: 1—The oxide coating consists of Cu2O with a superficial coating of CuO providing the ambient oxygen pressure exceeds the equilibrium pressure for the coexistence of Cu2O and CuO.² The following sequence of phases is then Cu/Cu2O/CuO/O2 (gas). The Cu2O consists of large crystals that have no relation to the orientation of the metal crystals, except for a very thin layer adjacent to the metal." The CuO consists of very fine crystals randomly oriented. If the oxygen pressure is below the equilibrium pressure for the coexistence of Cu2O and CuO, the coating consists of Cu,O only. 2—The rate-determining factor in the parabolic oxidation of copper is the diffusion of Cu+ ions through the Cu,O layer.4,6,7 The Cu+ ions are accompanied by electrons to maintain electrical neutrality. The mechanism of the reaction at the Cu2O/CuO interface and the method of growth of the CuO is in some doubt. 3—On copper, there are three reported pressure effects: (a) At pressures below 0.3 mm Hg oxygen pressure, the oxidation rate increases directly with pressure.', ' .Vxygen starvation at the surface may account for this effect. (b) At oxygen pressures from 0.3 to 63 mm, the oxidation rate increases as the 7th root of the oxygen pressure providing the temperature is such that only Cu2O is present in the film. (c) At pressures from above the equilibrium pressure for the coexistence of Cu2O and CuO (varies with temperature) to atmospheric pressure, the oxidation rate is independent of the oxygen pressure.' Equipment In order to determine the oxidation rates of metals in an oxidizing atmosphere at pressures up to 400 psi, the equipment is somewhat different than for low pressure work as is shown in Figs. 1 and 2. A Leeds and Northrup Micromax recording controller (A) is used to control the temperature of the Ni-chrome furnace winding in conjunction with a Micromax electric drive unit. The drive unit adjusts a 20 amp Variac (variable transformer) to control the power input into the Nichrome furnace winding. Due to the "self heating" of the sample by oxidation, frequently encountered in oxidation rate studies, it is essential that the sample temperature be measured independently. This is done by means of a series of six chromel-alumel calibrated thermocouples located spirally around the oxidizing metal sample. Each thermocouple is partially shielded from the direct radiation of the furnace wall by

Jan 1, 1954

By W. R. Webb, M. O. Peterson

WHEN men drive haulage equipment ranging up to 22 tons in an open pit operation, they must live with the realization that their safety is dependent upon the machines they drive and how well they operate them. The hazards inherent in their jobs must be recognized, met, and defeated. It comprises a never ending struggle toward perfection-an almost un- obtainable goal. The Jones & Laughlin Benson Mines, at Adirondack State Park in New York, created a safety program which resulted in only one three day lost time accident from April 1948 to April 1952. At the very start of the program, management of the open-pit operation recognized the hazards existing at Benson. The program was designed to meet each danger. With a knowledge of the problem faced, the process of minimizing each facet was planned along lines of maintenance of equipment and training of personnel. Its success is evident. In the ever-present struggle, care and maintenance of machines and application of experience to new equipment design are mainstays. Truck Haulage Benson produced 2.9 million tons of crude iron ore and 1.6 million tons of waste in 1951. To do the job, truck mileage reached 500,000 miles. The tremendous mileage emphasized to safety planners, the fact that the more work done, the greater the possibility of risk in haulage operations. Instrumenting the aim of the safest equipment possible is a methodical servicing program. Like other segments of the drive, the servicing program is based on greater production with fewer accidents. Every truck is serviced at least once per eight-hr shift. Examination includes inspecting and tightening wheel studs, checking tires, steering apparatus, lights, brakes, wipers, heaters, fire extinguishers, and refueling. A running history of the equipment's operating life is kept in the form of service and maintenance records. Machine operators are constantly on the alert for malfunctioning of units. At the first sign of trouble the truck is returned to the garage for exchange. No truck functioning incorrectly is kept on the line, regardless of its shift check schedule. The program resulted in a reduction of the number of costly overhauls and cut down the number of haulage accidents. Miscellaneous Mobile Equipment Auxiliary units, operating within the pit, have presented definite safety problems. The highest accident rate in the pit occurred on trucks carrying water and bits to the churn mills. The weight and awkwardness of bits and drill stems, combined with remote delivery points were direct causes of numerous accidents. Here, the problem has been one of equipment handling, rather than haulage. All air compressors for secondary drilling are truck mounted, facilitating mobility. In addition to making it easier to move the equipment, truck mounting has eliminated many of the hazards connected with relocating machinery. By making air compressors independent of other units, drilling operations have been speeded up considerably. Unseen rocks in the path of moving vehicles are a constant source of tire damage. At Benson the problem has been met by supplying each loading crew with a bulldozer for cleanup operations. The pitman directs the dozer operation, and when truck drivers back into loading areas, he serves as an extra set of eyes. Modern Truck Garage Provides Drive-Through Service Simplicity is the essence of any preventative maintenance program. At Benson, a modern garage, with a drive-through service bay simplifies servicing. Shift inspection of the 22-ton haulage units is accomplished with minimum delay and maximum thoroughness. Major repair work and periodic overhauls are done in the repair section of the truck garage. Crane facilities for handling heavy assemblies ease the job and add to the safety factor. Other mobile machinery,

Jan 1, 1952

By J. E. Miller, W. E. DeVaney, L. Stroud

During a recent phase study of a natural gas, two stable equilibrium liquid phases were observed at temperatures below —200°F and pressures above 200 psi. This paper reviews the published literature on the occurrence of multiple equilibrium liquid phases and presents analytical data for the vapor and two equilibrium liquid phases of the liquefied natural gas at five experimental conditions. In addition, data for 30 conditions of two-phase equilibria are included. INTRODUCTION The low-temperature phase behavior of gases, most of which contained helium, has been investigated in the laboratories of the Helium Activity for many years. Since 1952, experimental studies of these systems have been continuous as part of the research program at Amarillo, Tex. Because of their value to private industries interested in participating in the Helium Conservation Program, several "Open File" reports containing phase equilibria data for heliurn-bearing natural gases have already been released by the Helium Activity. A paper containing information on the general phase behavior, operating criteria and extensive vapor-liquid data for two helium-containing systems was recently published.2 Additional publications presenting experimental data on the phase relationships of various gas systems are now in process and will be available in the near future. PREVIOUS EXPERIMENTAL WORK Although the formation of multiple liquids has been reported for various systems, to our knowledge this paper is the only substantiated evidence of a vapor-liquid-liquid equilibria in a naturally occurring gas. In 1940, Vink, Ames, and others13 reported the presence of two liquid phases in a hydrocarbon system consisting of mixtures of crude oils, solvents and natural gas. Eilerts and co-workers; published data on the recombined fluids from a gas-condensate well. This condensed gas, containing approximately 76 per cent methane and 24 per cent ethane-plus, exhibited two distinct liquid phases. Weinaug and Bradley 14 observed "unusual" phase behavior in a reservoir mixture. These workers postulated that the anomalous phase behavior was due to the "imminent formation of a second liquid phase". Botkin, Reamer, Sage and Lacey 1 studied two California crude oils that exhibited multiple phases. Kohn and Kuratal0 recently reported two equilibrium liquid phases in the methane-hydrogen sulfide system. Roof and Crawfordl1 and Eakin, et a16 also have reported experiments with binary systems that formed two stable equilibrium liquid phases. APPARATUS AND PROCEDURE A U. S. Bureau of Mines Phase Equilibrium Apparatus was used in conducting this study. The apparatus and procedures employed in its operation have been previously described3 and will not be repeated in detail ill this report. Briefly, the apparatus consists of a windowed cell which can be maintained within ±0.5°F for temperatures between room temperature arid -320°F. Pressure within the cell can be maintained within 0.1 per cent of gauge reading up to 800 psig. Equilibrium vapor and liquid samples are obtained in special containers4 for analysis by a mass spectrometer. Although the accuracy of the analyzer is about ±0.1 mol per cent, the reproducibility of the phase-equilibrium apparatus is considered relatively poor. Values reported from methane and nitrogen are considered accurate to ±l.0 and ±0.6 mol per cent. Data for ethane-plus in the vapor are accurate within 0.2 mol per cent; liquid-phase data for this aggregate compolnent are accurate within 1.5 mol per cent. For helium in the vapor phase, the analytical data are accurate within 0.2 mol per cent; liquid-phase analyses for this component were obtained by the charcoal adsorption method described by Frost8 and are accurate within 0.006 mol per cent. All of these references to the accuracy of reported values are conservative estimates based upon a statistical treatment of reproducibility data obtained with the apparatus.

By F. W. Glaser, Benjamin Post

A LTHOUGH most transition metals form a wide variety of boride compounds, the existence of only one zirconium boride, ZrB2, had been established prior to this investigation.' The crystal structure and some properties of a hitherto unreported zirconium boride, ZrB12, are described in this paper. Only one other dodecaboride of a transition metal, UB12, has been reported up to the present.' Chemical analysis of the new compound showed 44 pct Zr and 56 pct B, compared with 41 pct Zr and 59 pct B computed for ZrB12. The difference is within the range of error of the analytical method employed. ZrB12 shows marked metallic properties. It is obtained as a fine black powder. Measurements of electrical resistivity were made at —79°C, + 22°C and +64°C. At 22°C the electrical resistivity is approximately 60 microhm-cm. Over this range the temperature coefficient of resistivity is +0.00162. The thermal conductivity at room temperature is 0.122 watts per cm per "C. The product of the electrical resistivity and thermal conductivity is therefore 8.05, which is not far from the normal Wiedemann-Franz ratio (approximately 7.5 at room temperature). These measurements were made on hot pressed samples which were not always high density specimens. The hardness of ZrB12 on the Rockwell A scale varies between 92 and 92.5. Crystal Structure Determination Single crystals of ZrB12 of a size suitable for X-ray diffraction analysis could not be obtained and powder samples had to be used. Filtered Cu radiation was used throughout. Powder diagrams were indexed on the basis of a face-centered cubic unit cell. After correction for film shrinkage, a Bradley and Jay extrapolation³ to ? = 90" indicated that a, = 7.408 ±0.002A. The volume of the unit cell is 406.5A.V he assumption that there are four "molecules" of ZrB12 per unit cell leads to an X-ray density of 3.63 g per cc. The measured density is 3.7 g per cc (as measured by the immersion method). Relative intensities of reflections were determined by integrating the intensities of diffraction peaks using the count register of a North American Philips wide range spectrometer. Intensities measured in this way showed good agreement with photographic intensities estimated visually using multiple film techniques. The usual Lorentz, polarization, and multiplicity corrections were applied to the observed intensity measurements. There are striking similarities between ZrB12, and UB12. The unit cell of the latter is also face-centered cubic and contains four molecules. a, = 7.473, compared with 7.408 for ZrB12. The radius ratio rB/rU is 0.57; rB/rZr is 0.54. In both ZrB12, and UB12 the four metal atoms in each unit cell are in special positions; only the boron positions need be determined. The latter may be inferred from the extent to which diffraction of X-rays by the 48 boron atoms reinforces or weakens the diffraction by the metal atoms. This effect is relatively much greater in the case of the zirconium compound. In their determination of the crystal structure of UB12, Berthaut and Blum' assumed holohedral symmetry (space group Oh5 , Fm3m) and reported that the U atoms are in positions 4(a): 000; 01/2 1/2; ½ 0 ½ ; ½ ½; the boron atoms were reported to be in positions 48(i) with x = 1/6: ½xx; ½xx; x½x; x½x; xx½; xx½; ½xx; ½xx; x½x; x½x; xx½; xx½

Jan 1, 1953

By J. L. Carne

ORE control is a matter of planning and supervision based on a foreknowledge of the content and distribution of ore. The Inspiration orebody is predominately a copper-sulphide blanket, overlain by an oxidized zone of copper silicates, copper carbonates, and barren capping. Most of the ore is treated by leaching, and the optimum requirement of this method is the goal toward which the mining schedule is aimed. Both open-pit operations and underground mining are used. The problems of ore control at Inspiration are: 1-maintenance of metallurgical balance, 2-conservation of oxide ore, and 3-mining out of the orebody at an average grade which parallels that of the reserve figure. Prior to the fall of 1926 all of the Inspiration division ores were treated by flotation, but the mixed ores of the Live Oak-Keystone section carried too large a proportion of copper in the form of chrysocolla for satisfactory flotation. For this type of mixed ore the leaching process now in use had been worked out, and the plant was put into operation in the fall of 1926. The process is known as the ferric sulphate leach, and the leaching solvents contain both ferric sulphate and free sulphuric acid. Sulphide copper in the form of chalcocite is leached by the ferric sulphate, and the oxidized copper minerals are dissolved by the sulphuric acid. From the beginning of operations to the present time the plant has treated some 67 thousand tons of ore having an average copper content of 1.142 pet, of which 0.605 pct has been in the form of oxidized copper minerals. The plant is currently being operated at the rate of 11,500 tons per day, 7 days per week. However, this tonnage is produced in 6 days of mine operation. The average current grade is approximately 1 pct copper, of which about 50 pct is present as oxidized or acid-soluble copper. Close control of metallurgical procedures is a vital factor in operation of the plant and is in turn dependent upon careful regulation of feed. An excess of sulphide copper requires the presence of more ferric sulphate in the leaching solvents. On the other hand, an excess of ferric sulphate in the presence of a low sulphide feed seriously reduces the efficiency of electrolytic precipitation in tank house operations. This condition must be avoided at all costs. An additional factor must be considered. It is known that the sulphide content is predominant in the ore which remains in the reserve. To maintain the necessary sulphide-oxide proportion, so that the entire reserve will mine out at both a grade and a sulphide-oxide ratio that will be permissible throughout the remaining life of the property, it is obvious that the oxide reserve must be currently preserved to as great an extent as possible. Fortunately much of the oxide reserve is found in the open-pit operation. This happy circumstance adds flexibility to the procedure and makes it possible to maintain the close regulation necessary to insure best overall results, both mining and metallurgical. The two ore streams from the pit and underground operations join at the coarse-crushing plant, and proper control must be exercised before the ore reaches this point. The open pit is currently providing about 55 pet of the ore and underground operations the balance of production. Both operations are under a single superintendent so that the closely interrelated problems may be more readily controlled. The least flexible of the two producing units is the underground mine, where the mining method is block caving. Although a block of ground may be undercut and developed, characteristics of the material determine its caving action. The ore in the chutes must be drawn. The area currently mined from underground is in a zone predominately sulphide and is generally

Jan 1, 1952

By F. Weinberg

In developing a mechanism for the solidification of metals from the melt, it has been proposed that solidification proceeds by the growth of platelets parallel to close packed planes. The evidence for this is based primarily on observations of decanted interfaces of lead1,2 and tin on which platelets 1 to 10 µ thick4 were observed. In recent observations of decanted eutectic alloys, 5,6 it was found that the eutectic structure on the decanted surface was markedly different than that of the bulk material, with the surface structure extending approximately 10 µ behind the interface.' This suggested that, at least for these experiments, a residual liquid layer 10 µ thick had been left on the decanted interface, which solidified subsequent to decanting. If a similar thickness of residual liquid was left on the decanted surfaces in the lead and tin observations referred to above, then it is questionable to what extent the observed platelets can be related to the solid-liquid interface before decanting. The purpose of the present investigation was to measure the thickness of the residual liquid layer on a decanted surface of tin, using relatively standard decanting procedures. The technique used was to add approximately 200 ppm of Tl204 (PI) to the melted portion of a high purity (99.999 pet) bar of tin, which was being progressively melted from one end, and then decant during melting. Since only the melt contained the radioactive tracer, the activity emanating from the decanted surface could be used as a measure of the thickness of the residual liquid layer. Progressive melting was carried out in the same fashion as single crystal growth, namely, in a horizontal graphite boat, in an argon atmosphere, using a moving furnace. The decanting was done in two ways; 1) removing the furnace and suddenly dropping the melt end of the boat, and 2) suddenly jerking the solid away from the liquid by the action of a falling weight (estimated peak acceleration 3 x 105 cm per sq sec), using a split graphite container. In all cases the melt was vigorously agitated by bubbling argon through it. The activity of the decanted surface was measured through an aperture 1.5 cm by 0.5 cm in a lead shield with an Anton tube geiger counter. Assuming that the active layer on the surface had the same concentration of Tl204 as the decanted liquid, the thickness of the layer could be determined from the measured activity of the decanted material, and the relationship between activity and material thickness. The latter was determined by rolling some of the decanted material into foil and measuring the activity of multiple layers of the foil. The activity At of material of thickness t (in mm) was determined to be A, = Ao(1 - e-22.5t) where Ao is the activity of the bulk material. The results of the measurements of the thickness of the residual liquid layer for six decants are given in Table I. The variation in t is attributed to variations in the decanting procedure and the rate of melting, the latter being difficult to control because of the vigorous agitation of the liquid. The rate of melting was in the order of 2 cm per hr, estimated from the position of the solid-liquid interface during melting. The results indicate that a residual liquid layer of the order of 10 µ in thickness is left on the decanted interface in agreement with the observation on eutectic alloys referred to above. If the mixing of the liquid during melting is not complete, as was

Jan 1, 1962

By C. van der Poel

When oil is displaced from a horizontal formation by another fluid of lower density, the latter tends to override the former in the shape of a tongue owing to gravity segregation. This gravity tongue has an adverse influence on the oil recovery. If the fluids are miscible, diffusion (mixing) takes place at the interfacial boundary of the gravity tongue. This mixing should have a favorable effect on oil recovery. The report describes a laboratory study of the magnitude of the mixing zone under various conditions, so as to assess the effect of diffusion on oil recovery both in laboratory experiments and under actual field conditions. The technique used enables visual observation and measurement of the size of the mixing zone in transparent glass-powder packs. The results show that in experiments in small models and cores the width of the mixing zone may well be of the same order of magnitude as the height of the model. In such cases oil recovery is favorably affected by mixing. It can further be concluded that, under conditions prevailing in the field, mixing of the injected fluid with reservoir oil is equal to that caused by molecular diffusion alone, eddy-mixing not taking place to any appreciable extent. A simple calculation, then, shows that molecular diffusion is too small for a beneficial effect to be expected from the injection of miscible fluids in horizontal or nearly horizontal reservoirs unless pay zones are thin. INTRODUCTION This paper gives results of experiments made on the mixing which occurs when a miscible displacement is carried out in a horizontal reservoir. This mixing takes place at the interfacial boundary of the gravity tongue formed when the lighter injected fluid overrides the oil present in the reservoir. The object of the experiments was to simulate the field case where, for example, propane with a viscosity of 0.075 cp under reservoir conditions displaces an oil of viscosity 0.6 cp. In the experiments the lighter fluid had a viscosity of about 1 cp and the heavier one a viscosity of about 8 cp, so as to obtain the same viscosity ratio. In order to enable the results to be compared with those published in the literature, a set of experiments with viscosity ratio equal to one was also performed. EXPERIMENTAL TECHNIQUE The technique developed for the purpose enables the width of the mixing zone to be studied as a function of time and place. A glass-powder pack is saturated with a water-glycerine mixture of suitable viscosity, which represents the reservoir fluid. The pack is then rendered transparent by dissolving sufficient ammonium thiocyanate in the mixture to obtain a solution with a refractive index matching that of the glass powder. Alkaline water to which phenol-phthalein has been added is used as the lighter and less-viscous displacing fluid. In those places where mixing or diffusion of the two liquids occurs, the slightly acidic ammonium-thiocyanate solution neutralizes the alkali in the water, and the glass pack shows up white against the red-colored invading water. If a black cloth is hung over the back of the apparatus, the transparent part of the glass pack appears black. In this way the position of the two phases and the transition zone between them is clearly visible, as shown in Fig. 1 (where the red-colored invading water is the grey-shaded zone lying uppermost). In all experiments the amount of alkali in the water was chosen such that the upper contour corresponded to a concentration of 5 per cent of the dense liquid. The lower contour is determined by the size of the glass grains and the thickness of the pack and, consequently, varies from experiment to experiment. Corresponding concentrations of the dense liquid range from about 97 per cent for packs of small grain size (permeability = 1 darcy) to about 95 per cent for those with large grains

By J. Spreadborough, D. LaW. King, E. Anderson

Tmzsile tests were performed on Armco iron samples, at various ternpe.ralures and strain rates, ocer a wide range of grain sizes. Analysis of the data suggests that the plot of the lower yield stress, against d-1/2,where 2d is the acerage grain diameter, is not linear (as is often assumed) but is concave toward the d. axis over the range of d-from 7 to 53 . The different values of the parameters obtained by other workers can be explained, in part at least, by the observed curvature. This curvalure is shown to be consistent with a model of yielding based on dislocation pile-ups; however, the values of obtained by fitting our data to this model differ appreciably from the values generally reported. The equation proposed by Cottrell, viz.: is a plausible empirical fit to the experimental results. The purpose of this paper is to comment on the validity of the widely used linear relationship first proposed by all' and Petch and coworkers2"4 between ay, the lower yield stress, and 2d, the average grain diameter, for bcc metals, viz.: Many workers, see Refs. 2 to 7 and Table 11, have fitted this equation to their experimental results and have obtained acceptable fits over the relatively narrow range of grain sizes used by most of them. Indeed, in some cases, so few data points were available that any more sophisticated fit would have been irrational. In most of the interpretations,'-' oi is thought to be a measure of the friction stress accompanying dislocation movement, and ky was originally inter- preted as a measure of the dislocation locking but is now believed by Cottrell" to be a function of the dislocation creation rate. In the "unpinning" theories, k, is equated to where od is the unpinning stress and 1 is the average distance from the boundary of the grain where yielding is taking place to the nearest dislocation source in an unyielded grain. Other considerations (see, for example, Refs. 11 and 12) lead to equations with a similar form to [I] where different meanings may be attributed to the parameters. While there are doubts as to the physical significance of the parameters i and k, they continue to be used by many workers; interpretations of the variations in the behavior of ferrite materials following certain treatments, e.g., aging,'3 neutron irradiation,14 have been given frequently in terms of these parameters. Some theories of the mechanical behavior of bcc metals are based on this relationship. We have investigated experimentally the oy - d-'lZ relationship for Armco iron over a wider range of grain sizes and with more data points than those given in published results. The analysis of our data suggests that the oy—d-'" relationship is not linear but is in fact concave towards the d-'I2 axis. RESULTS AND DISCUSSION The experimental work was carried out on 3-mm-diam Armco iron rods which were prepared by wire drawing from 5-mm-diam rods. By annealing in vacuum at temperatures between 7000 and 1200°C for various times, grain sizes from 7 to 20,000 grains per sq mm were obtained, the grains in all cases being regularly shaped. Grain sizes were measured by lineal interceptand by area methods; only specimens with Amax/A values of 3 to 6 were used in the Petch-Hall plots (where A is the average area of a grain and Amax is the area of the largest grain observed). For all the specimens used, the number of grains in a cross section exceeded 50, which should be adequate to avoid grain size effects.'= Tensile tests were performed at 296", 219, and 17l°K, using

Jan 1, 1969

By H. J. Ramey

The wellbore acts as a storage tank during drawdown and build-up testing and causes the sand-face flow rate to approach the constant surface flow rate as a function of time. This effect is compounded if non-Darcy flow (turbulent flow) exists near a gas wellbore. Non-Darcy flow can be interpreted as a flow-rate dependent skin effect. A method for determining the non-Darcy flow constant using this concept and the usual skin effect equation is described. Field tests of this method have identified several cases where non-Darcy flow was severe enough that gas wells in a fractured region appeared to be moderately damaged. The combination of wellbore storage and non-Darcy flow can result in erroneous estimates of formation flow capacity for short-time gas well tests. Fortunately, the presence of the wellbore storage eflect permits a new analysis which can provide a reasonable estimate of formation flow capacity and the non-Darcy flow constant from a single short-time test. The basis of the Gladfelter, Tracy and Wilsey correction for wellbore storage in pressure build-up was investigated. Results led to extension of the method to drawdown testing. If non-Darcy flow is not important, the method can be used to correct short-time gas well drawdown or build-up data. A method for estimation of the duration of wellbore storage effects was developed. INTRODUCTION In 1953, van Everdingen and Hurst generalized results published in their previous paper3 concerning wellbore storage effects to include a "skin effect", or a region of altered permeability adjacent to the wellbore. Later, Gladfelter. Tracy and Wilsey4 presented a method for correcting observed oilwell pressure build-up data for wellbore storage in the presence of a skin effect. The method depended upon measuring the change in the fluid storage in the wellbore by measuring the rise in liquid level. To the author's knowledge, application of the Gladfelter, Tracy and Wilsey storage correction to gas-well build-up has not been discussed in the literature. It is, however, a rather obvious application. Gas storage in the wellbore is a conlpressibility effect and can be estimated easily from the measured wellbore pressure as a function of time. Several approaches to the wellbore storage problem have been suggested. As summarized by Matthews, it is possible to minimize annulus storage volume by using a packer, and to obtain a near sand-face shut-in by use of down-hole tubing plug devices. Matthews and Perrine have suggested criteiia for determining the time when storage effects become negligible. In 1962, Swift and Kiel' presented a method for determination of the effect of non-Darcy flow (often called turbulent flow) upon gas-well behavior. This paper provided a theoretical basis for peculiar gas-well behavior described previously by Smith. Recently, Carter, Miller and Riley observed disagreement among flow capacity k,,h data determined from gas-well drawdown tests conducted at different flow rates for short periods of time (less than six hours flowing time). In the original preprint of their paper, Carter et al. proposed that the discrepancy in flow capacity was possibly a result of wellbore storage effects. Results of an analytical study of unloading of the wellbore and non-Darcy flow were recorded by carter.14 In the final text of their paper, Carter et al.!' stated that they no longer believed wellbore storage was the reason for discrepancy in their kgh estimates. In view of the preceding, this study was performed to establish the importance of non-Darcy flow and well-bore storage for gas-well testing. In the course of the study. a reinspection of the previous work by van Everdingen' and Hurst' was made, and the basis for the Gladfelter, Tracy and Wilsey' wellbore storage correction was investigated and extended to flow testing. WELLBORE STORAGE THEORY As has been shown by Aronofsky and Jenkins,11-12 Matthews," and others, flow of gas can often be approximated by an equivalent liquid flow system. The following developnlent will use liquid flow nomenclature to simplify the presentation. Application to gas-well cases will be illustrated later. First, we will use the van Everdingen-HursP treatment of wellbore storage in transient flow to establish (1) the duration of wellbore storage effects, and (2) a method to correct flow data for wellbore storage. DURATION OF WELLHORE STORAGE EFFECTS When an oil well is opened to flow. the bottom-hole pressure drops and causes a resulting drop in the liquid level in the annulus. If V. represents the annular volume in cu ft/ft of depth, and p represents the average density of the fluid in the wellbore, the volume of fluid at reservoir conditions produced from the annulus per unit bottom-hole pressure drop is approximately: res bbl-- (V, cu ft/ft) (144 sqin./sq ft) psi -(5.615 cu ft/bbl)(pIb/cuft) ........(I)

Jan 1, 1966

By W. L. McMorris, A. H. Brisse

IN the last several years the coal industry has intensified its effort to solve the growing problem of cleaning and recovering fine mesh coals. On one hand these has been increasing civic pressure for cleaner streams, and on the other hand there has been increasing production of fine mesh coal, resulting directly from adoption of the modern mining methods so essential to the economy of the coal mining industry. Cleaning fine coal with the same precision possible with coarser coals is a difficult task, and for coals finer than 200 mesh it has been impractical. Furthermore, the inclusion of —200 mesh material in the final product markedly increases costs of de-watering and thermal drying, which are necessary steps if coal is to meet market requirements. Consequently these extreme fines have generally been wasted. As a result, problems have been created in many districts because there has not been enough area for adequate settling basins. Wasting of coal in the -200 mesh slimes may account for a loss in washer yield equivalent to 2.0 to 2.5 pct of the raw coal input. With rising mining costs the value of such a loss is constantly increasing and a need for a better solution to the fines problem becomes more pressing every day. From an operating viewpoint, also, continuous removal of extreme fines from the washing plant circuit permits good water clarification practice, improving significantly the overall cleaning efficiency. The obvious desirability of recovering a commercially acceptable coal from washery slimes prompted U. S. Steel Corp. to investigate the merits of the Convertol process developed in Germany." Although this process has been used commercially in Europe for some time, little if any consideration has been given to its possible adoption in the U. S. until very recently. Fundamentals of the Convertol Process: In the Convertol process, droplets of dispersed oil are brought into intimate contact with the solids suspended in the coal slurry to be treated. This contact causes oil to displace the water on the surface of the coal by preferential wetting, or phase inversion, after which the coal particles are allowed to agglomerate in a manner permitting their re- moval from the slurry by centrifugal filtration. The clay and other particles of mineral matter suspended in the slurry do not have the affinity for oil the coal particles have. Consequently the oil treatment is preferential to coal to the extent that more than 95 pct of the oil used reports with the clean coal recovered. Figs. 1 through 3 will clarify the steps involved in the process. Fig. 1 shows the suspended material in the slurry to be treated, which is a thickened product containing 40 to 45 pct solids. Oil is now injected into the slurry under vigorous agitation to produce good oil to coal contact conditions, which result in preferential oiling of the coal particles. These coal particles are then permitted to agglomerate by gentle stirring in a conditioner to form flocs, as shown in Fig. 2. At this point in the process the agglomerated oiled coal can be washed and partially dewatered on a vibrating screen, as shown in Fig. 3. Finally, the washed flocculate can be further dewatered in a high-speed screen basket centrifuge or in a solid bowl centrifuge. Commercial Application of the Convertol Process in Germany: The original Convertol process was developed by Bergwerksverband zur Verwertung von Schutzrechten der Kohlentechnik, G.m.b.H., a German research organization controlled by the Coal Operators Assn. of the Ruhr Valley. The process as reduced to commercial practice in Germany' is shown in Fig. 4. In this process a thickened slurry (40 to 45 pct solids) mixed with a predetermined percentage of oil is fed from a surge tank to the phase inversion mill. After the phase inversion step, the slurry is usually discharged directly to a highspeed screen centrifuge. From 3 to 10 pct oil is used, depending on type of oil, size consist of coal to be recovered, and operating temperature. The top size of fine coal cleaned in Germany by the Convertol process is limited by the size of the openings in the centrifuge screen basket. Any mineral matter coarser than the basket opening, which is generally 60 to 80 mesh, must remain with the oiled coal. If the coal fines have been effectively cleaned down to about 80 mesh, the cleaning performance of the process is practically unaffected by the presence of coarse coal particles. However, since recovery of coal much coarser than 80 mesh is mow economical by conventional methods, it normally becomes more costly to allow substantial percentages of this coarse coal in Convertol process feed. Where the general plant layout does not permit effective cleaning of coal sizes down to 80 mesh or lower. there is some justification for a coarser Con-

Jan 1, 1959

By Ross C. Anderson, William I. Weisman

THE manufacture of anhydrous sodium sulphate or salt cake from natural deposits in the United States has been in general somewhat of a marginal undertaking. Competition from foreign sources and from large quantities of byproduct sodium sulphate produced domestically in the manufacture of hydrochloric acid and other chemicals has existed and continues. For example, most of the sodium sulphate produced is a byproduct or co-product in the manufacture of hydrochloric acid through the reaction of sodium chloride with sulphuric acid. In recent years, many manufacturers of rayon have installed equipment to recover sodium sulphate from waste spin bath liquors; today this is an important source. Before World War II large quantities of sodium sulphate were imported from Germany. In 1949 imported material from Europe again appeared on the domestic market. Natural sodium sulphate from Canada in substantial quantities also enters the United States markets. Despite this kind of competition, numerous attempts have been made to exploit various natural deposits of sodium sulphate in this country, but only a very few of these have survived economically over a period of years. One of these few operations is the plant of the Ozark-Mahoning Co. located 13 miles south of Monahans in West Texas. Several factors contributing to the successful life of this plant may be summarized as follows: 1—Geographical location. Monahans is reasonably close, freightwise, to the Kraft paper mills in Texas, Arkansas, and Louisiana; the Kraft paper industry is the greatest consumer of sodium sulphate in the United States. 2—Availability of natural gas as low cost fuel. Proximity of the natural gas fields of West Texas has been a tremendous asset, as the availability of low-cost natural gas is to all industry throughout the Southwest. 3—The nature of the deposit. The occurrence of sodium sulphate brines in southeastern New Mexico and West Texas has been very well described by Lang,' who writes that the brines are found in the Castile formation of the Delaware basin. Here weathering has altered the anhydrite so that a relatively porous gypsiferous zone overlies a dense impervious mass of anhydrite. This porous zone provides traps where percolating ground waters that have picked up soluble salts may lodge. These traps or pockets are the natural brine reservoirs exploited at Monahans. Although several hundred wells have been drilled, currently some 25 wells serve to supply brine to the plant. All are within 1 1/2 miles of the plant and are conveniently tied together by an electric power system serving electric motors driving the pumps. Having the raw material in the form of a brine which can be pumped from shallow wells makes possible much simpler and more efficient handling than if it were in form of solids. By contrast, other deposits of sodium sulphate, such as those in Arizona, Nevada, and North Dakota, are in the form of the solid minerals, thenardite and mirabilite, which present somewhat more of a mining and mineral dressing problem.' The largest producer of sodium sulphate from natural sources in the United States is at Searles Lake, Cal., and there a brine also is utilized. 4—Water. Substantial quantities are needed for cooling towers and for operation of gas engines. An area underlain with brine is not a promising source of fresh water, but fortunately, after a long search, an adequate supply was found nearly two miles from the plant. It may be appropriate to discuss briefly the grades of sodium sulphate offered on the market. Salt cake is the name usually applied to the grade of sodium sulphate used by the Kraft paper industry. It may be a low analysis byproduct, 95 to 97 pct sodium sulphate, with as much as l 1/2 to 2 pct residual acid, or it may be a natural product. Usually salt cake is considered a low grade product, but a great deal of a higher grade of material is marketed under this name. The specifications for glassmakers' salt cake are somewhat higher than those of the paper industry, usually requiring 98 pct sodium sulphate. Technical anhydrous sodium sulphate is a high grade material and usually exceeds 99 pct sodium sulphate. It finds the biggest market in the textile industry and is used as a builder in some synthetic detergents. Glauber's salt, Na2SO4. 10H20, is usually of high purity. Preferred for some uses, it normally has been recrystallized from an anhydrous salt. A unique manufacturing process has been developed at Monahans. This process results in the production of an exceptionally high grade of salt cake, and qualifies for nearly all uses, including many which specify the technical anhydrous grade. All of the finished product, which is very white, passes a 10-mesh U. S. Standard screen, and is retained on a 200-mesh U. S. Standard screen. It is over 99 pct Na2SO4 with main impurities being sodium chloride and magnesium sulphate. Iron content is less than 0.01 pct. As mentioned, the raw material at Monahans is a brine drawn from wells. Attention was first attracted to this location because a so-called alkali

Jan 1, 1954

By E. Miller, K. Komarek, W. Johnson

The activity of aluminum in solid Cr-A1 alloys has been measured by an isopiestic technique between Cr-A1890' and 1126" and 13 and 80 at. pct Al. The integral free energy of mixing has a minimum value of —5600 cal per g-atom at 59 at. pct Al. The maximum solid solubility of aluminum in chromium was determined to be 43 at. pct Al, and the composition limits of the compounds CrA14, Cr4A19, and Cr5Al, at 1000"~ were found to be 79 to 80, 66 to 70, and 59 to 63 at. pct Al, respectively. The thermodynamic properties of the Cr-A1 system have been investigated as part of a thermodynamic study of aluminum-transition metal systems.172 Little information is available on the equilibrium properties of the Cr-A1 system. The heats of formation of solid Cr-A1 alloys have been determined by Kubaschewski and Haymer at 600" and low-temperature specific heat data have also been obtained.~ More extensive work has been performed on the phase diagram, and a compilation has been provided by Hansen and Anderko,~ their phase diagram at elevated temperatures being essentially based on the work of Bradley and LU.~ The high-temperature portion of the phase diagram shows an intermediate phase CrA14 decomposing peritectically at 1018°C and existing at 82 at. pct A1 at 1000°C. They also identified the compounds with solubility limits of 72 to 75 at. pct A1 at 1000°C, and Cr5A1,, existing at 61 at. pct A1 at 1000°C. The maximum solid solubility of aluminum in chromium at 1000°C was found to be 46 at. pct Al. These elevated-temperature data were obtained by examination of quenched samples and were considered as less precise than the lower-temperature data. Koester, Wachtel, and Grube7 have revised the phase diagram as a result of their magnetic susceptibility and X-ray study. The results of this work differ appreciably from those of Bradley and Lu at temperatures above 800°C. The CrA1, compound is given as existing between 79 and 81 at. pct A1 at 1000°C, and they do not indicate the presence of a CrA13 phase reported by Bradley and Lu. They also report the compound Cr4Alg as having solubility limits of 66 to 70 at. pct A1 at 1000°C, while Bradley and Lu show this compound stable only up to 870°C. Koester et al. state that the high-temperature modification of the compound Cr5A18 is stable down to 1125"C, and not 980°C as stated by Bradley and Lu, and that the low-temperature modification of Cr5Al, has a range of homogeneity of 58 to 63 at. pct A1 at 1000°C. They also report that the maximum solid solubility of aluminum in chromium is 43 at. pct A1 at 1000°C. APPARATUS AND EXPERIMENTAL PROCEDURE An isopiestic method was employed which has been successfully applied to the determination of aluminum activities in solid ~e-All and Ni-Al alloys. Alloy specimens were held at different positions in a temperature gradient and were equilibrated with aluminum vapor from an aluminum reservoir kept at the temperature minimum of an impressed thermal gradient in a closed alumina system. Diffusion of aluminum into the specimens occurred until equilibrium was reached, at which the partial pressure of aluminum in each of the specimens was given by the vapor pressure of the pure aluminum reservoir. The activity of aluminum referred to liquid aluminum as the standard state in a given equilibrated sample at temperature T could therefore be expressed by: vapor pressure of pure aluminum at _ the temperature of the reservoir Vapor pressure of pure liquid aluminum, at specimen temperature T Since both the temperature of the aluminum reservoir and the specimen temperatures were determined experimentally, and the vapor pressure of pure aluminum is known as a function of temperature,' the activity of aluminum in a given aluminum alloy of known composition could be calculated. Initial runs were made with samples consisting of pure chromium chips placed in alumina crucibles. These runs exhibited large inconsistencies, indicating that equilibrium was not attained. High aluminum content Cr-A1 alloy powders were therefore substituted for the pure chromium specimens. The starting composition of the alloys was adjusted through experimentation until the concentration change necessary to attain equilibrium was small. In this manner, consistent results were obtained in reasonable times. SPECIMEN PREPARATION Alloy specimens were prepared from chromium of 99.997 pct minimum metallic purity: with 0.028 to 0.038 pct H, 0.0002 pct N, and 0.27 to 0.46 pct 0 (Aviquipo, Inc.). The aluminum had a purity of 99.99+ pct and the following impurities: 0.003 pct Cu; 0.002 pct S; 0.002 pct Fe; 0.001 pct Pb; 0.001 pct Ga (Aluminum Corp. of America). Alloy powders were prepared from weighed mixtures of chromium and aluminum by double-arc melt-

Jan 1, 1969

By M. Cohen, D. J. Blickwede

Quantitative observations concerning the carbide phases in high speed steel are of importance for two general reasons: (1) the carbides, being inevitable constituents of the final structure, exert a direct influence on the properties of the steel; and (2) a substantial proportion of the total alloy content is tied-up in the carbides, and hence the extent of their solution on austenitizing governs the composition of the steel matrix. The latter relationship has a vital bearing on the response of the steel to tempering as well as on its performance in subsequent service. Accordingly, in the course of a long-term study of the behavior of high speed steels, the authors were confronted with the problem of securing quantitative data on the carbide phases. The obvious method for acquiring such information is to isolate the car-bides from the steel and subject them to chemical, X ray diffraction and other measurements. There are well-known extraction techniques which involve the chemical or electrolytic solution of the less noble matrix (ferrite, marten-site or austenite), thus leaving a residue of the carbide phases. However, the results obtained must be scrutinized carefully1,2 since the carbides may be affected by the chemical or electrolytic action. It is the purpose of the present paper to describe the experiments leading to an electrolytic-extraction technique for quantitatively isolating the carbides from both I and hardened high speed steel. Particular attention is paid to the amount, as well as the composition, of the carbides so that the matrix analysis becomes ascertainable by subtraction from the overall steel composition. Illustrative results are given for the M-2 grade of tungsten-molybdenum steel. Review of the Literature The chemical method of dissolving the matrix selectively with respect to the carbides makes use of dilute non- oxidizing reagents such as hydrochloric or sulphuric acid. Although this simple procedure has led to the determination of the cementite composition,3,4 it achieved only limited success because of the interaction between the acid and the carbide residue. Some of the carbides may not only be destroyed in this way, but the hydrogen released is likely to remove part of their carbon as hydrocarbon gases. The electrolytic technique of isolating carbides has the advantage of rapidly dissolving the specimen (anode) in the presence of less reactive solutions than are practicable with the chemical method. This reduces the possibility of chemical attack on the carbides, and furthermore, the hydrogen evolved during the electrolysis is released at the cathode which is not in close proximity to the carbides. The common electrolytes adopted for this purpose are hydrochloric and sulphuric acids.5-l1 Aqueous solutions of ferrous salts have also been used.12,13 A considerable advance in experimental technique was introduced by Treje and Benedicks14 who developed a double-compartment cell for electrolytic extraction, the anode and cathode chambers being separated by a porous diaphragm. A solution of 15 pct sodium citrate, 2 pct potassium bromide and 1 pct potassium iodide was selected for the anolyte, while the catholyte consisted of a 10 pct solution of copper sulphate, with copper serving as the cathode. This type of cell has a number of desirable characteristics: 1. The anolyte has a pH value close to 7, at least at the beginning of the run. 2. The iron that dissolves from the anode-specimen forms a water-soluble complex ion with the citrate, thereby preventing the precipitation of iron hydroxide (which would contaminate the carbide residue) despite the neutrality of the solution. 3. Copper deposition instead of hydrogen evolution occurs at the cathode, and this avoids an increasing concentration of hy-droxyl ions which (in an otherwise neutral solution) might cause the precipitation of insoluble hydroxides. 4. Contamination of the anode chamber by copper sulphate is inhibited by the porous diaphragm. Houdremont and coworkers15 applied the above method (with the further refinement of excluding oxygen during the electrolysis, washing and drying) to the extraction of carbides from a series of plain carbon steels after various heat treatments. They had quantitative success only with specimens in the annealed condition, and concluded that the size and shape of the carbide particles play an important role in the isolation process, with large spheroids exhibiting the least tendency to decompose during the electrolysis. Up to the present time, the citrate double-cell has not been used to any extent for isolating the carbides of high alloy steels, apparently on the grounds that the complex carbides are more resistant than cementite to attack in the simpler acid electrolytes. In particular, Bain and Grossmann7 and Gulyaev10.10a have employed the hydrochloric acid cell for their investigations of the carbides in high speed steel.* It will be demonstrated here that this type of cell is capable of yielding quantitative results in the case of high speed steel, and actually has certain advantages over the more complicated double cell. However, in order to provide a rigorous test of the quanti-tativeness of electrolytic procedures for the problem at hand, both methods were studied in considerable detail.

Jan 1, 1950

By J. Brett, L. Seigle, L. Castleman, T. Montelbano

Impurity-induced low-temperature recrystallization of cold-worked tungsten was inuestigated with emphasis on the influence of nickel on the reaction. Palladium, nickel, aluminum, manganese, platinum, and iron greatly lower the recrystallization temperature of doped tungsten, which zs normally very high, but the recrystallization temperature of electron-be am zone-refined tungsten wzre is slightly raised by conlacl with nickel. Recrystallization can be induced at low temperature by the presence of solid nickel on the surface of doped tungsten wire, but apparently not by exposure to nickel vapors alone. Approximately 200 ppm of Ni dijjused into 10-mil wires at 1200 from a deposit of nickel on the surface produced total recrystallization, whereas more than 600 ppm of Ni could be absorbed frotn a vapor source without altering the fibrous structure of cold-worked tungsten. Once initiated, nickel-induced recrystallization required a continued source of' nickel for propagation of the recrystallization front. The solubility of nickel in fibrous 10-mil W wire was approximalely 500 ppm at 1150' C, and the activation energy for penetration of the recrystallization front was 52 kcal per mole. In many applications the usefulness of tungsten depends on critical control of its structure. Cold-worked tungsten with the fibrous structure developed by suitable thermo-mechanical treatment has a low, but technologically significant, ductility. It has long been known1 that traces of nickel, and perhaps other metals, are profoundly deleterious in doped tungsten, because they induce recrystallization at low temperature, which produces a brittle, equiaxed grain structure. This effect appears to be an exception to the general observation that recrystallization is impeded and the recrystallization temperature raised by the presence of impurities.2"9 Previous studies7-'' of the annealing and recrystallization of tungsten wire have divided the phenomenon into prior recovery stages, primary recrystallization and secondary recrystallization. The present investigation is concerned principally with primary recrystallization which is defined here as the replacement of the fibrous structure of deformed tungsten by equiaxed grains. The objective of this study was to explore the nickel-induced recrystallization reaction in tungsten and attempt to elucidate its mechanism. As well, an effort to define which other elements give rise to low-temperature-induced recrystallization was carried out. EXPERIMENTAL PROCEDURE The procedure adopted for these experiments was essentially to bring nickel and other elements into diffusive contact with cold-worked tungsten wires. The process of recrystallization was followed as a function of time and temperature by light and electron microscopic observations. First the influence of nickel on the recrystallization temperature of arc-melted, zone-refined, and variously doped tungsten wire was determined by electroplating a deposit of nickel on the surface of the wire and annealing at a variety of temperatures for 3 hr. The chemical analyses of the tungsten wires used in this investigation are given in Table I. The surface of the tungsten wire was etched with Murakami's slution' and approximately 0.005 in, of Ni was deposited from a Watts-type low pH bath14 for the conditions of these experiments. Variations in plating thickness from about 0.001 to 0.005 in. had no discernible influence on the resulting structures. The wires were then annealed in an atmosphere of dry hydrogen to establish the recrystallization temperature. Concurrently, un-plated specimens were annealed to establish the recrystallization characteristics of nickel-free wire. The criterion of recrystallization was that the fibrous structure be completely replaced by equiaxed grains after a 3-hr treatment of temperature. This provided more reproducible results than use of the first recrystallized grain or a fixed proportion of re-crystallized structure as the critical observation. The structures encountered in longitudinal and transverse sections were examined by both light and electron microscopy at magnifications up to X32,000 using parlo-dion-carbon replicas shadowed with platinum for the latter method. Second, the influence of a variety of metals on the recrystallization temperature of 0.010 in. D alumina-silica doped tungsten wire, AW136-64, was determined. The elements were applied by electroplating whenever possible. Alternatively, they were vapor-plated on the tungsten wire and a greater thickness built up by coating with a dispersion of metal powder in nitrocellulose lacquer. Elements not amenable to either of these procedures were merely slurry coated on the tungsten. The recrystallization temperature was determined as above. Third, the nickel-induced recrystallization process in doped wire was studied more closely by electroplating 8 mils of Ni on 65-mil alumina-silica doped tungsten wire, AW153-NS10, and exposing the wire to temperatures of llOO°, 1200°, or 1300°C for various times in a hydrogen atmosphere. A circular recrystallization front, 'Onsisting of equiaxed grains, developed at the periphery Of the coated tungsten wire, and the advance of this front into the fibrous interior was studied. These experiments employed relatively coarse 0.065 in. D wire because the 0.010 in. D wire recrystallized too quickly to permit observation of the pene-

Jan 1, 1969

By D. H. Desy, L. C. Fincher

The magnesium-rich end of the Mg-Ti phase diagram was investigated. The liquidus, solidus, and solvus boundaries to 1 pct Ti were established. All alloys were prepared by saturating molten magnesium with titanium in a consumable titanium crucible under inert gas maintained at 230 psig. The liquidus of the Mg- Ti system was determined by analysis of dip samples taken from 700° to 1300°C under equilibrium conditions in a pressurized inert atmosphere furnace and by analysis of small ingots rapidly poured and quenched from 1400° to 1500°C. The solubility of titanium in magnesium ranged from 0.018 wt pet Ti at 700°C (0.012 wt pet at 650°C by extrapolation) to 1.035 wt pet Ti at 1500°C. The solidus for compositions ranging from 0.03 to 1.00 wt pet Ti was determined to be 650° ± 1°C by thermal analysis. The titanium solid solubility values ranged from 0.08 wt pet at 350°C to 0.19 wt pet by extrapolation to 650°C. The freezing reaction is peritectic. No intermetallic compounds were found in the system; the phase in equilibrium with molten magnesium saturated with titanium was found to be titanium with magnesium in solid solution. Solid titanium will dissolve at least 1.32 wt pct Mg. PREVIOUS investigations of the Mg-Ti system have shown considerable disagreement on the solubility of titanium in liquid magnesium. Furthermore, the solid solubility of titanium in magnesium has not been well established. Liquidus curves for previous work and for the present investigation are shown in Fig. 1. Aust and Pidgeon1 used a dip-sampling method on molten magnesium held in equilibrium with solid titanium under a protective atmosphere to determine the solubility and found that it ranged from 0.0025 wt pet Ti at 651°C to 0.015 wt pet Ti at 850°C. Eisenreich2 introduced titanium into molten magnesium by means of TiCL4 adsorbed on BaCl2. Ingots were then cast at various temperatures. Making the assumption that only the titanium dissolved in magnesium at the time of casting was soluble in H2SO4, Eisenreich determined the solubility of titanium in molten magnesium to range from 0.003 wt pet at 655°C to 0.115 wt pet at 800°C. Eisenreich also determined the solid solubility of titanium in magnesium to be 0.015 wt pet at room temperature and 0.045 wt pet at 500°C. Since the solid solubility just below the freezing temperature for the bulk of the alloy was much larger than the liquid solubility just above the freezing temperature, Eisenreich concluded that the freezing reaction was peritectic. Obinata et al.3 equilibrated molten magnesium with titanium in hermetically sealed titanium containers which were then furnace-cooled. The titanium content of the magnesium was then determined and found to range from 0.170 wt pet at 700°C to 0.85 wt pet at 1200°C. No intermetallic compound was found in the system. The Armour Research Foundation4 determined two points on the solvus by electrical resistivity methods: 0.00057 wt pet at 200°C and 0.0008 wt pet at 300°C. At higher temperatures, data were meaningless with no trends observable. The authors of this report believed that the lack of significant data at the higher temperatures was due to variations in specimen geometry, although there was no positive evidence to verify this supposition. The present investigation was undertaken to clarify the uncertainty in both the liquidus and solvus of the magnesium-rich end of the Mg-Ti system. EQUIPMENT AND MATERIALS The equipment used in this investigation, with some modifications, was essentially that used by Crosby and Fowler5 in their determination of part of the Mg-Zr phase diagram. The equipment, as modified for this work, is shown in Fig. 2. It consists of a sealed furnace chamber which can be pressurized with inert gas so that melts can be made above the boiling point of magnesium at atmospheric pressure. Melts are made by induction heating in a titanium crucible which, after diffusion of sufficient magnesium into the walls of the crucible to saturate the titanium at the sampling temperature, comprises the solid phase in equilibrium with the molten magnesium. Dip samples may be taken with the sampling tube, or the entire furnace may be tilted so that ingots may be poured into a mold in the side chamber. The principal difference from the earlier apparatus is in the thermocouple, which in the present equipment is enclosed in a protection tube and immersed directly in the melt. The tips of both the thermocouple protection tube and the sampling tube, which dip into the melt, are made of high-purity titanium. The 4 1/2-in.-long titanium tip of the sampling tube is threaded into a steel tube, O in Fig. 2, which extends through the top of the furnace. To determine whether the temperature at the tip of

Jan 1, 1969

By G. H. Anderson

H. R. HANLEY*—I have been asked to discuss briefly the development of rotating cathodes for the electrolytic deposition of cadmium. The earliest recorded use of rotating cathodes was by Hoepfner at Frufurt, Germany about sixty years ago. He elec-trolized zinc chloride solution using diaphragms to separate electrodes. In the early experimental work of the Bully Hill Copper Mining and Smelting Co., Shasta County, Calif., rotating aluminum cathodes 4 ft in diam were used in the electrolysis of an acid zinc sulphate solution. Finished cathodes weighing up to 400 lb were produced. Because of mechanical difficulties, this type of cathode was abandoned for zinc, but was later used for cadmium because of the relative smoothness of deposit in comparison with stationary plates with comparable current densities. Cadmium sponge which forms on the cathode at moderate current densities (without special treatment) is entirely eliminated by a slow rotation. The rate of rotation of the cathode has an effect on the mechanical nature of the deposit. A high rate of rotation concentrates the adhering electrolyte on the shaft; a moderate rate appears to concentrate on the cathode a short distance out from the shaft tending to corrode the deposit in the form of a ring. At a very slow rotation (2 to 3 rpm) the adhering electrolyte gravitates nearly vertically, thus avoiding the cutting ring referred to above. The true explanation for the smoother deposits obtained on rotating cathodes may not be given definitely as the numerous factors involved are not thoroughly understood. Smooth deposits are obtained when the orderly growth of the metal crystals in the cathode lattice are disorganized. Thus the crystals form and grow for a very short interval when they are arrested and a new crystal forms. The continued growth of the original crystals provides large crystals and a rough deposit. Also if the acidity of the electrolyte is low, hydrogen gas bubbles adhere to the deposit. As the cathode is rotated the gas surface is brought into the atmosphere where they burst; thus the deposit is made on a surface relatively gas-free. An aluminum hub distance piece was riveted to each aluminum disk 4 ft in diam, slipped on a 4 1/2 in. steel shaft and pressed tight to prevent acid electrolyte seeping through to the shaft. The 9-cathode assembly was supported on insulated bearings. Electrical contact to the shaft was made through what was equivalent to a copper pulley. Sufficiently high conductivity brushes were placed on the face of the pulley to lead the current to the cathode bus bar. The assembly was driven by a link belt contacting a sprocket insulated from the shaft. The lead anodes were semicircular and supported on porcelain insulators placed on the bottom of the cell. Two anodes were provided for each cathode to permit an 8-in. space between them without increasing the ohmic resistance. This ample spacing permitted easy stripping of deposit with the assembly in place. Cathode cadmium was melted under 650 W cylinder oil. After casting, the primary slabs were remelted under molten caustic soda and cast into pencils 1 1/32 in. in diam. Rotating cathodes for deposition of cadmium are used at Risdon, Tasmania, and at Magdeburg, Germany. W. G. WOOLF*—This paper is very-interesting to me because in our work at the Electrolytic Zinc Plant of the Sullivan Mining Co. we had an exactly similar problem—that is, a method of producing cadmium from our purification residue, the recovery of the contained copper as a copper precipitate which could be sent to a copper smelter and the production of merchantable cadmium. It is interesting to me, not knowing of the work of the Risdon people, how closely we approximate them in their main metallurgy, diverging at several interesting steps which I would like to discuss for just a moment. For example, at Risdon they oxidize their purification residue. In our practice we take the current residue as it is produced in the purification department of the zinc plant and process it in the cadmium plant. The only oxidation that it obtains is the oxidation in the presses, the dumping of the presses and the collection and transportation of the residue to the cadmium plant. We find that the leaching of that residue does not necessarily require the oxidation step that the Risdon people evidently find necessary. The discussion of oxidation comes in again in the matter of the treatment of the precipitated cadmium sponge with zinc dust which again at Risdon is oxidized but which we do not attempt to oxidize except as it oxidizes itself in the storage. There is a partial oxidation which cannot be avoided, as Mr. David-sou pointed out, but we make no attempt to attain a complete oxidation and we dissolve the cadmium sponge in the sul-

Jan 1, 1950

By T. M. Morris, W. E. Horst

W. E. Horst—In regard to the flotation rate being described as "first orcler" for flotation of quartz particles below 65 p in size (or any size studied in this work) in this paper, it appears that the authors' conception of rate equations is not in agreement with cited references. A first order rate equation has as one of its forms the following: a In.=a/a-x=kt where a = initial concentration, a—x = concentration at time t, t = time, and k = constant. The constant, k, has the dimension of reciprocal time which is similar to the specific flotation rate, Q. described by Eq. 2 in the authors' article, as has been previously discussed by Schumann (Ref. 1 of original article). The plotted data presented in Fig. 4 of the article utilizes the specific flotation rate, Q (min.'); however, there is not adequate data given to indicate the order of the rate equation which describes the flotation behavior of the quartz system studied. Results from the experimental work indicate that the relationship between rate of flotation (grams per minute) and cell concentration (provided the percent solids in the flotation cell is less than 5.2 pct and the particle size is less than 65 p) is described by an equation of the first order (R, = k c+", n being equal to 1 in this size range) and the use of the first order rate equation does not apply. Similarly the relationship for other particle size ranges studied is expressed by equations of the second or third order depending on the magnitude of n. T. M. Morris—The authors are to be commended for the experiments which they performed. As they state in their discussion the concentration of collector ion In solution did change with change in concentration of solids in the flotation cell. Since for a given slze of particle, flotation rate increases with concentration of collector until a maximum is reached, the effect of concentration of particles in their experiments was to vary the concentration of collector ions. A collector concentration which insures maximum supporting angle for all particles eliminates the unequal effect of collector concentration on various sized particles and the effect of size of particles and concentration of particles upon flotation rate could be more clearly assessed. I believe that if the authors had increased the concentration of collector to an amount sufficient to attain a maximum supporting angle for all particles they would find that the specific flotation rate of particles coarser than 65 p would be constant with change in the concentration of solids in the flotation cell, and that a first order rate would apply to the + 65 as well as to the —65 p sizes. It might also be discovered when this change in collector concentration was made that the maximum specific rate constant would be shifted toward a coarser fraction than when starvation quantities of collector are used since this practice favors the fine particles and penalizes the coarse particles. P. L. de Bruyn and H. J. Modi (authors' reply)—The authors wish to thank Professor Morris for his kind remarks and for mentioning the influence of equilibrium collector concentration on flotation rate. With a collector concentration sufficient to insure maximum supporting angle for all particles, a first order rate equation may indeed be found to be generally applicable irrespective of size. Such a concentration would, however, lead to 100 pct recovery of the fine particles and consequently defeat the essential objective of the investigation to derive the maximum information on flotation kinetics. To establish absolutely the validity of any single rate equation for a given size range, the ideal method would be to work with a feed consisting solely of particles of that size range. Use of such a closely sized feed would also eliminate the possibility of the interfering effect of different sizes upon one another. The authors do not believe that increasing the collector concentration would shift the maximum specific flotation rate (Q) towards a coarser fraction. Experimentation showed Q to be independent of solids concentration for all particles up to 65 µ in size, whereas the maximum value of Q was obtained in the range 37 to 10 p. Professor Morris contends that the addition of starvation quantities of collector favors fine particles at the expense of coarse particles, but the reason for this is not entirely clear to the authors. The comments by Mr. W. E. Horst are concerned only with the concept of the term "first order rate equation." According to the usage of this term in chemical kinetics, time is an important variable, as is shown in the equation quoted by Mr. Horst. All the experimental results reported by the authors were obtained under steady state continuous operations when the rate of flotation is independent of time. To be consistent with the common usage of the "first order rate equation," it would be more satisfactory to state that under certain conditions the experimental results show that the relation between flotation rate and pulp density is an equation of the first order.

Jan 1, 1957

By C. C. Harris

The characteristics of some common size distribution equations are critically discussed. A generalized form of several well-known size distribution equations is obtained from a differential equation describing statistical distributions. The equation contains three parameters and can describe the major features of size distributions in the fine and the coarse size regions. A graphical method for its implementation is provided. The application of this and other equations to sets of data are compared both for the quality of fit and from a comminution kinetics viewpoint. If a narrow size range of a brittle material is broken sufficiently to obliterate the feed sizes, but not so severely that excessive secondary breakage occurs, a plot of cumulative fraction by weight undersize (Y) vs. sieve size (X) on a log log grid (sometimes called the Gates-Gaudin-Schuhmann plot)1-3 gives a straight line of slope ~ 1 over much of its range. On closer inspection, deviations in the extreme coarse range covering perhaps 10 to 30% of the total sample may be apparent (frequently, a change in slope from ~ 1 to a value different from unity) together with over-all slight irregular departures from a smooth line. One model of breakage postulates that the same fracture pattern persists throughout all size ranges.4 The fracture pattern is characterized by the slope of the line on a log log grid. Accordingly, a distribution of sizes broken in the manner specified earlier is expected to produce a size distribution having the same slope as that of a broken narrow size range. Additionally, the slight irregularities mentioned above should even out in the summation process, giving a smooth straight line of slope ~1 on a log log plot. This idealized state of affairs does not, however, describe the distribution of a multi-event process such as that for a tumbling mill product. On the average, these curves (plotted again log log) tend to have a slope in the fine region different from and usually less than unity,5 while the coarse size region curves with increasing slope for cases of mild reduction, and with decreasing slope when moderate or severe size reduction has occurred. In addition, there are usually slight irregular deviations from a smooth curve. Most curves display two distinct regions — fine and coarse — and a few curves show one or more intermediate regions. Feed size studies6,7 show an effect which theory is required to explain. For the same material, mill loading and other operating conditions, and the same time of grinding, plotting the dimensionless ratios Y vs. X/(feed size) does not reduce the size distribution data to the same curve. Y vs. X does not correlate the coarse region, but it can provide a crude correlation of the fine region which improves as size diminishes and as grinding time increases. The size distribution in the coarse region is somewhat more dependent on the feed size than is the distribution in the fine region wherein the degree of dependence diminishes as time proceeds; the distribution of sizes in the fine region are determined largely by the nature of the material and the comminution conditions. A comprehensive model of comminution must recognize that several different patterns or modes of breakage can occur in a mill; 5,8,9 that there can be some selection in that some size ranges are broken more than others; and that, while some particles may be the product of a single fracture event, or may even remain unbroken, others result from multiple rebreak-age. Thus, breakage in a tumbling mill is more complex than the Schuhmann4 model admits in that several different types of comminution micro-events* occur rather than just one type, and these events, though different in size scale, are of the same overall pattern as that which is visualized by the model. The concept of an average comminution micro-event has, therefore, a mathematical rather than a physical connotation, at least for tumbling milling. Equations with which to describe particle size distributions have been sought for over half a century.10-13 No equation presently in general use was first derived from an analysis of the statistical mechanics of breakage; whatever theoretical basis the existing

Jan 1, 1969

By M. C. Flemings, G. E. Nereo

General expressions are given to describe macro-segregation in castings and ingots which results from mass flow of solute-rich liquid to feed solidification and thermal contractions. Analytical solutions are given for solidification with planar isotherms (unidirectional and bidirectional heat flow). These solutions describe inverse segregation and centerline segregation. Numerical examples are given for A1-4.5 pct Cu alloy. In 1540, Vannoccio Biringuccio published one of the first references to macrosegregation, describing the problem of exudation and inverse segregation in the manufacture of bronze gun barrels.' Since then, a great many studies of macrosegregation have been reported. Recent work of particular engineering interest includes that of Marburg 2 and others:" on centerline segregation and other types of segregation in large steel ingots, and work of Adams,5 Scheil, 6 and Kirkaldy and youdelis7 on inverse segregation in nonferrous ingots. In most studies on this subject, the various types of macrosegregation have been treated as separate phenomena. For example, quite different mechanisms have been proposed for formation of centerline segregation, negative cone of segregation, inverse segregation, banding, and so forth. In this, and in several papers to follow, it is proposed that these as well as other types of macrosegregation result from the same basic mechanism and can be quantitatively described by the same basic equation. It has often been suggested that some types of segregation (such as centerline segregation and banding) occur as a result of buildup of solute at the tips of growing dendrites.2-4 ,8-10 As example, banding can be induced in centrifugal castings by mechanical vibration, and Northcott 10 suggests this might be due to the influence of the vibration on the boundary layer at the dendrite tips of the growing dendrites. However, in view of the extremely small boundary layer known to exist at the tips of the dendrites,11,12 any interpretation of macrosegregation based on this boundary layer is clearly incorrect. Note that experiment has shown that significant buildup of solute does not occur at dendrite tips in ingot solidification, but even if such buildup occurred the thickness of the enriched zone would only be the order of D/U where D is liquid diffusion coefficient and U is dendrite tip velocity. For usual casting or ingot solidification this solute-enriched layer is 10"3 cm, far too small to account, for example, for centerline segregation.11'12 It has also been suggested that convection in the bulk liquid (ahead of the advancing dendrites) might cause segregation by sweeping away the solute-rich boundary layer in front of the dendrites.3 However, since there is no significant boundary layer, this explanation must be incorrect. The convection might directly cause segregation by penetrating between the dendrite arms, and presumably in a rimming steel ingot it is sufficiently vigorous to cause some segregation in this way. Centerline segregation, however, cannot be interpreted as resulting from this convection since a sharply segregated zone is usually found near the centerline, with the bulk of the ingot being nearly of nominal composition. If convection in the bulk liquid were the direct cause, a gradual change in ingot composition over the entire cross section would be expected. It is known that sudden changes in convection of the bulk liquid during solidification can result in banding,14 but it is not clear that the banding results directly from the effect of convection on solute distribution. Changes in convection also affect thermal conditions in the liquid-solid region of a solidifying ingot. It will be seen later in this paper, and in a paper to follow, that macrosegregation is strongly influenced by these thermal changes. Recognizing that in some cases of ingot solidification (as in solidification of rimming steels) convection in the bulk liquid may have a direct effect on solute distribution, we neglect it in this paper and in the several to follow. We then derive general expressions describing macrosegregation which results from the mechanism of interdendritic flow of solute-rich liquid

Jan 1, 1968

By C. E. Ells, A. Sawatzky

The effect of neutron irradiation on tensile properties of the Zr-2.5 wt pet Nb-0.5 wt pet Cu alloy has been evaluated for integrated neutron fluxes up to 3 x 1020 n per sq cm (E > 1 Mev). Specimen temperature during irradiation was normally 300°C. The material was studied both in annealed and in quenched and aged conditions. When the alloy (fab-ricatedfrom sponge zirconium) is quenched from a temperature =40°C below the a + ß/ß transformation and aged 6 hr at 535oC, neutron irradiation up to the maximum studied has little effect 071 reduction in area, although there is a drop in uniform elongation and the yield strength is increased by = 25 pct. Conversely, irradiation of the alloy in an annealed condition can result in much greater changes in properties, with yield-strength increases of up to 200 pet. The dose dependence of irradiation hardening obeys the saturation equntion proposed by Makin and Minter to explain hardening in copper and nickel: Act = C[1 - exp(-Døt)/1/2 A rnodel is proposed to explain the effect of niobium content and metallurgical condition on irradiatiotz behavior. THE Zr-Nb alloys form a class of material susceptible to marked strengthening by quench and age heat treatment. With niobium concentrations as low as 2.5 wt pet, strengths can be developed which are double those of annealed zircaloy-2.1 Since the neutron-capture cross section of the Zr-2.5 wt pet Nb alloy is nearly identical to that of Zircaloy-2, significant gains in power-reactor neutron economy could be obtained by replacing stressed in-reactor components of Zircaloy-2 with the heat-treated Zr-Nb alloy. When the solution heat-treatment temperature is in the high (a + ß) phase, then the tensile properties of the quenched (and aged at 500°C) material have been shown to be relatively insensitive to neutron irradiation.1-3 Addition of small quantities of copper to the binary Zr-2.5 wt pet Nb alloy gives a useful reduction to the corrosion rate in air and carbon di- oxide,&apos; and a ternary alloy of composition Zr-2.5 wt pet Nb-0.5 wt pet Cu was chosen for one component in the Douglas Point Reactor. This application utilizes both the corrosion resistance to a moist air-carbon dioxide environment and the strength developed by a quench and age heat treatment. By suitable choice of solution heat treatment and aging temperatures, tensile properties of the ternary alloy can be made nearly identical to those considered as optimum for the binary alloy. One effect of the copper addition, however, is to give marked changes in the aging kinetics of the alloy.&apos; For this reason, it appeared that neutron irradiation might promote overaging in the ternary alloy, particularly at the elevated service temperature (=300°C). This paper describes the effect of neutron irradiation on the tensile behavior of the Zr-2.5 wt pet Nb-0.5 wt pet Cu alloy in several metallurgical conditions pertinent to its use as a reactor material. The metallurgical conditions included those for which aging occurs in the unirradiated material, and fully annealed conditions for which a higher degree of thermal stability could be expected. 1) EXPERIMENTAL Two batches of alloy were used, both made from sponge zirconium. The fabricator&apos;s analysis of principle constituents showed no significant difference between the two batches, Table I. The rod material was rolled to 1.5 in. diam, and then swaged to final sizes of 0.5 to 0.375 in. diam at nominal temperatures of 785" and 625°C for the AM and AS batches, respectively. Subsequent hydrogen analyses at CRNL confirmed that the hydrogen concentration of the as-received rod was indeed <20 ppm. However, it was found that the (a + ß)/ß transus for the AM material was approximately 25°C lower than that of the AS material, indicating rather more difference in oxygen concentration than given in Table I. Except for a small difference in yield-point behavior, the tensile prop-

Jan 1, 1965