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By Pedro Bolsaitis, Paul M. Sullivan

The activities of zinc in liquid Zn-A1 alloys in the temperature range of 1000' to 1160°K were determined by means of the isopiestic technique. The results are in reasonable agreement with the previous values determined by the radioactive tracer dew point method. Slightly negative excess entropies of mixing were found. The measured activities suggest that the a function for these alloys is not a constant, as has frequently been assumed, but is better represented by two straight line segments of different slopes. THE thermodynamic data of Al-Z alloys have been the subject of investigation by many authors. However, in the recent compilation of such data by Hult-gren et al.,5 the conclusion is reached that none of the previous measurements are reliable or consistent with each other. Since then two new sets of measurements have been reported,2, 8 both laying claim to good accuracies, yet showing very significant disagreement in the measured activity coefficients of zinc in Zn-A1 alloys and in the magnitude and sign of the excess entropies of mixing. Information on the thermodynamics of the system is of particular interest for interpreting results of the Bureau of Mines research on refining of zinc by distillation of die cast scrap. The present study was undertaken as an independent check on the recent values obtained from dew point measurements 8 and electromotive force measurements.' The isopiestic method, first introduced by Herasy-menko,' was chosen because it is one of the few thermodynamic techniques which, in principle at least, is carried out under perfect equilibrium conditions. The disadvantage of the method is that data are obtained at various random compositions and temperatures, which makes the interpretation somewhat cumbersome. The random errors arising from temperature gradients and fluctuations appear to be comparable to those of other techniques, as evidenced by the magnitude of the estimated uncertainties in the calculated integral thermodynamic quantities. An advantage of the method is that each run provides a relatively large amount of data; thus, it is less time consuming than those methods where samples of each composition must be measured individually. EXPERIMENTAL PROCEDURE The activities of zinc in liquid Zn-A1 alloys were measured by the isopiestic method which uses the principle of the tendency toward equilibrium of a series of samples at various temperatures under an imposed vapor pressure of the more volatile component (i.e., zinc, in this case). The basic apparatus is shown in Fig. 1. The small graphite crucibles that contained the metal samples were 15 mm ID and 13 mm deep with approximately 3 mm wall thickness. Each crucible was notched at the top and bottom to allow easy passage of vapor from one to another. At the beginning of an experiment each crucible was weighed on an analytical balance. Zinc and aluminum of spectrographic purity (99.999 pct) were then weighed into the crucibles. The amounts of each metal added were such that initial compositions varied above and below equilibrium values. One crucible contained only pure zinc. After weighing, the crucibles were stacked with the pure zinc on the bottom (corresponding to the lowest temperature in the furnace) and richest aluminum alloys at the top. The entire stack of crucibles was then placed in the silica glass container "E" which was then sealed under vacuum. Sixteen to twenty calibrated Chromel-Alumel thermocouples were attached by wire along the length of the silica tube, one or more adjacent to each sample.

Jan 1, 1970

By L. O. Howard

R. HATCH, Garfield, Utah.-The object of the meeting, I believe, is to determine the proper chemical composition to insure long wear of a ball in a mill, This might also apply to rods. I feel that there is only one way of determining accurately the wearing qualities of balls in mills, and that is by actually wearing out 400 or 500 tons of different kinds of balls. Two things add to the wearing qualities of a ball: (1) the tenacity, with which the particular particles of iron or steel are cemented together; (2) the individual hardness of each particle. My experience is that a ball that has a Brinell of 550 to 650 will give comparatively long life. There is considerable difference of opinion as to the best steel and iron alloys necessary to produce a satisfactory grinding ball. Some favor chrome, some manganese and some nickel. Personally, I believe cast iron alloyed with chrome makes the best ball for small sizes; for large sizes (3 1/2 in. and up) steel alloyed with manganese is best. L. 0. HOWARD, Pullman, Wash.-How would this method apply to lining? A. KissocK, New York, N. Y.-I do not subscribe to that exactly. As I am connected with the Climax Molybdenum Co. you would hardly expect me to. We have been much interested in trying to work out this grinding-ball problem and have spent a great deal of thought and effort on it. As we are associated with the American Metal Co. and have a number of properties of our own, we are in position to try our ideas on ourselves first. We have tried different compositions, but have not done anything very remarkable with them yet, except that we have been able to say that the combination of chrome and molybdenum has given the best wearing ball. Mr. Hatch feels that iron is the best medium for grinding, but since toughness as well as hardness is a factor in wearability we feel that a well made steel is better for this purpose. Another difficulty with cast, or chilled, iron is lack of uniformity from day to day or from heat to heat and the impossibility of producing balls free from blow or shrinkage holes which materially affect their life. If cast iron is made hard it becomes brittle and lacks stretch or toughness. This prevents its use in the larger sizes, as breakage is a serious handicap to efficiency. We have tried hard and brittle balls and softer but very tough balls and have proved that maximum hardness, with sufficient toughness to prevent breakage, is the most important factor in resistance of a steel to abrasion. It is well known that chromium is one of the best hardening agencies for either iron or steel, and molybdenum is recognized as an element capable of introducing toughness. In other words, the proper combination of chromium and molybdenum permits unusual hardness with still sufficient toughness to stand up under severest impact. It is yet too early to give any actual mill results of this new combination and though we are proving our ideas at our own properties we have to depend on others to help us make the data more general and more worth while and would like to get some tests

Jan 1, 1928

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

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

Jan 1, 1953

Jan 1, 1939

By J. W. Putman, N. J. Grant, D. S. Bloom

SEVERAL recent determinations of the melting S point of pure chromium have been reported which give values of 1845°C1; 1895°C,² 1930°C,³ 1860°C,' and 1890°C.5 because of this wide spread of values, it appeared desirable to make one additional attempt to obtain a more accurate, reliable figure. bloom and Grantx recently reported a phase transformation in chromium:.--- it was desired to check this, too, in the course of checking the melting point. To accomplish this, a much higher purity chromium was required. Electrolytic chromium containing about 0.5 pct 0 was crushed to a finer size and was then annealed in highly purified, dried hydrogen at 1375°C for 100 hr. This treatment produced chromium with about 0.008 pct 0, 0.002 pct N, and negligible carbon. The balance of the impurities was 0.3 pct Fe, 0.03 pct Si, 0.004 pct S, and less than 0.001 pct Mo. This chromium was melted in a stabilized zirconia crucible under pre-purified argon, using induction heating. Temperature measurements were made with annealed wolfram-molybdenum thermocouples and a Leeds and Northrup Speedomax Recording Potentiometer. The thermocouples were annealed for 1 min in hydrogen at a temperature of about 2400°C. Each leg of the thermocouple was immersed in an ice-water mixture using mechanical connectors to the lead wires. The thermocouple tip was immersed in the molten chromium in a zirconia protection tube which introduces an error of about 3°C as a temperature drop through the walls of the tube. The weight of chromium was about 183 g. The dimensions of the melt in the crucible were about 1.25 in. diam x 2 in. high. The tip of the thermocouple was held about ½ in. from the bottom of the crucible. Two new thermocouples were used with the above set-up giving the results shown in Table I. Since this chromium is purer than that used by Greenaway, Johnstone and McQuillan,' by Carlile et al.,4 and other investigators,²,3 it is believed to be the more accurate. Thermocouple aging effects which are believed responsible for the high value of 1930°C³ were avoided in this work. This value of 1903°C is correct to about ±10°C. The right hand column lists the temperature of the a ? ß transformation on heating and the ß ? a on cooling.3 A sample curve is shown in Fig. 1. The value so determined is 1840°C + 15°C. Fig. 1 gives adequate evidence that there is a transformation in chromium at high temperatures.' References 'H. T. Greenaway, S. T. M. Johnstone, and M. K. McQuillan: High Temperature Thermal Analysis USing the Tungsten-Molybdenum Thermocouple. Journal Inst. Metals (November 1951) 19, p. 109. ²J. W. Putman, R. D. Potter, and N. J. Grant: The Ternary System Chromium-Molybdenum-Iron. Trans. A.S.M. (1951) 43, p. 824. ³D. S. Bloom and N. J. Grant: Chromium-Nickel Phase Diagram. Trans. AIME (1951) 191, p. 1009; Journal of Metals (November 1951). ' S. J. Carlile, J. W. Christian, and W. Hume-Rothery: The Equilibrium Diagram of the System Chromium-Manganese. Journal Inst. Metals (1949) 76, p. 169. 5G. Grube and R. Knabe: Ztsch. Elektrochemie (1936) 42, p. 793.

Jan 1, 1953

By Karl F. Peterson, H. K. Najarian, Robert E. Lund

R. E. Powers (Mellon Institute of Industrial Research, University of Pittsburgh, Pittsburgh)—Several of the processing methods at the Josephtown smelter might well be considered by plants producing iron blast furnace sinter. In making blast furnace sinter the objectives are much the same as at Josephtown: To produce a strong yet porous agglomerate which has a size consist in a preferred range. The emphasis however is on production rate rather than on the size or other quality characteristics of the sinter. Therefore the technique is entirely different. Blast furnace sinter plants attempt to make their product in one pass with a minimum recirculating load and without sizing treatment after the sinter leaves the machines. Many plants are beginning to feel that more attention paid to quality characteristics would make the product a more desirable blast furnace material. The pelletizing of very fine material before placing it on the bed is not deliberately done at iron sinter plants, although the installed equipment sometimes gives a simila; action. Such pelletizing seems to be a promising way of accommodating the down-draft sintering Drocess to very fine materials. he recirculating load at Josephtown is extremely high. Two plants' producing blast furnace sinter from raw material of comparable size have a recirculating load of about 100 pct of production. At Josephtown it is notable that the size and the rate of feeding of return fines are under control. This is not the case in most blast furnace sinter plants. The sinter slicer appears to be a worthwhile aid in effecting such control. It is similar in action to rakes and plows used at a number of plants, but it has the advantage that the sinter dislodged is positively removed and not left to the inefficient action of a stationary grizzly screen. Blast furnace size specifications for sinter are not at present so rigid as the Josephtown specifications. If the sizing of blast furnace sinter does become important, then the Josephtown crushing practice, in which a large recirculating load is maintained on the crusher in order that minimum fines be produced, may be of interest. H. K. Najarian (authors' reply)—We note that Mr. Powers appreciates some points that we tried to emphasize in our paper as being of importance in making zinc sinter of good quality and which may well be applied to iron blast furnace sinter. Fig. 2 shows the pelletized nature of the feed going on to a Dwight-Lloyd type sintering machine in our plant. Practically, the entire feed consists of more or less rounded particles which permit more uniform air passage through the charge, while the larger particles in the charge roll on to the surface of the grate, which helps to keep the grate openings from being clogged by excessive fines. An agglomerated charge of this character may preferably be made by rolling action while being mixed in a rotating drum and wetted by water sprays to bind the fine particles together and give the charge the desired moisture content. From our observations of several iron ore and blast furnace flue dust sintering operations, we believe that if the fines from the sinter discharged from the machines were to be recirculated and agqlomerated with the new feed, not only sinter of better quality but larger capacity from the machines may be realized.

Jan 1, 1952

R. E. Powers (Mellon Institute of lndustrial Research, University of Pittsburgh, Pittsburgh)—Several of the processing methods at the Josephtown smelter might well be considered by plants producing iron blast furnace sinter. In making blast furnace sinter the objectives are much the same as at Josephtown: To produce a strong yet porous agglomerate which has a size consist in a preferred range. The emphasis however is on production rate rather than on the size or other quality characteristics of the sinter. Therefore the technique is entirely different. Blast furnace sinter plants attempt to make their product in one pass with a minimum recirculating load and without sizing treatment after the sinter leaves the machines. Many plants are beginning to feel that more attention paid to quality characteristics would make the product a more desirable blast furnace material. The pelletizing of very fine material before placing it on the bed is not deliberately done at iron sinter plants, although the installed equipment sometimes gives a simila; action. Such pelletizing seems to be a promising way of accommodating the down-draft sintering Drocess to very fine materials. he recirculating load at Josephtown is extremely high. Two plants' producing blast furnace sinter from raw material of comparable size have a recirculating load of about 100 pct of production. At Josephtown it is notable that the size and the rate of feeding of return fines are under control. This is not the case in most blast furnace sinter plants. The sinter slicer appears to be a worthwhile aid in effecting such control. It is similar in action to rakes and plows used at a number of plants, but it has the advantage that the sinter dislodged is positively removed and not left to the inefficient action of a stationary grizzly screen. Blast furnace size specifications for sinter are not at present so rigid as the Josephtown specifications. If the sizing of blast furnace sinter does become important, then the Josephtown crushing practice, in which a large recirculating load is maintained on the crusher in order that minimum fines be produced, may be of interest. H. K. Najarian (authors' reply)—We note that Mr. Powers appreciates some points that we tried to emphasize in our paper as being of importance in making zinc sinter of good quality and which may well be applied to iron blast furnace sinter. Fig. 2 shows the pelletized nature of the feed going on to a Dwight-Lloyd type sintering machine in our plant. Practically, the entire feed consists of more ,or less rounded particles which permit more uniform air passage through the charge, while the larger particles in the charge roll on to the surface of the grate, which helps to keep the grate openings from being clogged by excessive fines. An agglomerated charge of this character may preferably be made by rolling action while being mixed in a rotating drum and wetted by water sprays to bind the fine particles together and give the charge the desired moisture content. From our observations of several iron ore and blast furnace flue dust sintering operations, we believe that if the fines from the sinter discharged from the machines were to be recirculated and agqlomerated with the new feed, not only sinter of better quality but larger capacity from the machines may be realized.

Jan 1, 1952

By Philip R. Strand, O. F. Stewart

Vermiculite is the name generally applied to the group of hydrated ferromagnesian aluminum silicates that are characterized by the ability to expand when heated. This process, called exfoliation, results in a lightweight product of commercial value. Most uses of vermiculite are for the expanded material. The chief markets are in construction, agriculture, and horticulture, with lesser uses in general industry. Composition and Properties Vermiculite, in its natural state, has the characteristic micaceous habit, a perfect basal cleavage which causes splitting into thin laminae that are soft, pliable, and inelastic. The structure of vermiculite is basically that of a talc. The prominent monoclinic crystal faces are often marked by lines at 60° and 120°. Hardness varies from 1.5 to 2 or more; specific gravities are between 2.1 and 2.8; color varies from almost clear to amber, bronze, brown, green, or black. Vermiculite feels like talc, especially when wet. Although much research has been performed on the chemical and structural composition, there is not yet complete agreement on the exact formula. This is to be expected when different workers have examined the many different varieties. Vermiculite is not considered to be a single mineral species but a family of related minerals. The structural formula for a trioctahedral vermiculite may be written: (H20)-(Mg,Ca,K)-(A12,Fe,Mg)-(Si,A1,Fe)4O10 (OH) 2 Hydrobiotite also occurs with vermiculite and is usually considered a vermiculite for commercial uses. When heated quickly to elevated temperatures, vermiculite expands by exfoliating at right angles to the cleavage into wormlike particles. The name vermiculite is derived from the Latin vermiculare, to breed worms. This characteristic of expansion is the result of the mechanical separation of the layers by the rapid conversion of contained water to steam. The decrease in bulk density of commercial grades is usually approximately 10 times, from 50 to 5 lb/ft3, but varies depending on the quality, size, and furnace efficiency. Individual flakes may expand up to 30 times. Vermiculite may also be expanded by soaking in chemicals such as hydrogen peroxide, weak acids, and other electrolytes. Color change during expansion is dependent upon the type of vermiculite and furnace conditions. Heating in an oxidizing atmosphere produces a dull gray or tan color, whereas a reducing atmosphere can produce a bronze or gold color. The expansion of the vermiculite crystal results in large pores being formed between the platelets. Thus, exfoliation makes available a large increase in void volume which is important in the application of vermiculite as a chemical carrier. Mathieson and Walker (1954) state vermiculite must be regarded as a true clay mineral. The characteristic properties of the mineral, such as high cation exchange capacity, organic complexing ability, and variable interlamellar distance are very similar to those of montmorillonite. The cation exchange capacity of vermiculite is one of the highest of all the clay minerals. The interplatelet space is accessible to penetration by some electrostatically neutral molecules. Water and glycerine are two common substances whose molecules may be so imbibed. In the natural state and under normal atmospheric conditions, water occupies the spaces between the silicate layers. The crystal d-spacing is near 14.2A. By differential thermal analysis, it has been determined that the water

Jan 1, 1983

By W. L. Worrell

R. C. Gifkins (CSIRO)—In this paper evidence is put forward to support the idea of grain boundary shearing in aluminum at 4.2°K and the phenomenon is explained in terms of a low-temperature "equicohesive temperature". It is stated that these findings show that grain boundary shear cannot be ruled out in any situation by temperature arguments alone. We believe, from our own recent study of "apparent grain boundary sliding'' at temperatures below 0.45 Tm, that it can be ruled out on temperature arguments alone.45 Our experiments were made principally with magnesium and a Ms-A1 alloy ("Magnox A12"). Careful examination of offsets of marker lines or steps at grain boundaries produced by deformation at room temperature (-0.3 Tm) showed many of these to result from curvature over narrow zones along the grain boundaries. A significant residuum did, however, appear as a sharp offset or step. It was found that the mean value of this step rose to a small value during the first 0.5 to 1 pct strain and then remained at this level with further strain. Moreover, exactly the same values were obtained (at the same stress) at 75°C instead of 21°C. That is, in this range of temperature the "apparent sliding" was not temperature-sensitive. At 125°C and above there was sliding which increased with strain and which was temperature-dependent. When this temperature-dependent sliding was used to calculate the sliding to be expected at room temperature, this underestimated the "apparent sliding" by a factor of 104. The conclusion drawn is that the "apparent sliding" consists of shear localized in a zone of a width measured perhaps in microns, whereas it seems that true sliding occurs on the boundary surface.46 A model for such localized shear has been developed in general terms, following a similar model of Urie and Wain.47 Other strong evidence for low-temper- ature sliding has been based on the offsets of marker lines consisting of a substructure seen using the electron microscope to resolve these.48 We have repeated this work and found that the effects can be accounted for in terms of cracks in an oxide film which is produced when the substructure is etched up; these cracks form over zones of shear rather than at actual interfaces. However, in aluminum at room temperature (-0.3 Tm) there is no "apparent sliding" which is optically detectable. We suggest that, when the temperature is much lower (and possibly the rate of strain higher, too), as in the experiments of Chin et al., then aluminum behaves like magnesium at room temperature, and a narrow zone of shear develops to accommodate differences in strain across the grain boundary. Such a zone could well give rise to triple-point cracks. It is hoped to investigate these suggestions further. B. Y. Chin, W. F. Hosford, Jr., and W. A. Backofen (authors' reply)—It is interesting to have Dr. Gif-kin's comments, although it is somewhat difficult to reply in detail without the reference containing the work that he describes. Apparently though, he does find a low-temperature temperature-independent sliding that would seem to be related to the observations reported here. Perhaps some of the difficulty has semantic origins, growing out of the distinction between ('true sliding" and "apparent sliding".

Jan 1, 1965

By I. Havenaar

EXPERIMENTAL DATA In an article by C. K. Ferguson and J. A. Klotz,1 experiments on the filtration of drilling muds under borehole conditions are discussed. Experimental data on mud filtration through the wall and the bottom of the hole are presented. From the data on bottom-hole filtration it was concluded that the filtrate does not flow freely into the formation, but that the pores of the formation are plugged by the mud. A quantitative interpretation of the data can be civen, by using a formula for bottom-hole filtration, dehved below. This formula is based on the following assumptions, 1. Each time a blade of a drag bit, or a cone of a roller bit, moves along the bottom of the hole, the mud cake is completely removed. 3. A new mud cake is immediately formed on the freshly produced surface, and losses of "whole" mud into the formation are negligible (this is equivalent to an immediate plugging of the pores). 3. The filtration of the mud on the bottom of the hole follows the classic law: V = A +1—(Eq. I), where t is the time required to yield a volume of filtrate V, A is the surface area of filter cake, and C is a constant. The application of this equation means that any eroding effect of the mud stream on the mud cake is neglected. The formula for the calculation of the volume of filtrate, Q,, flowing in one second through the hole bottom (diam. d cm), when using a bit with n cones or blades rotating at a rate of rn revolutions per second, is derived as follows: The mud cake is formed on the bottom of the hole in the time t =1; the filtrate volume V which passes n through the bottom In this time 1s given by Eq. 1: After1/nmsec the mud cake is removed. In one m second this process takes place nm times. Therefore the volume of filtrate, obtained in one second is given by This equation has now been applied to the experiments of Ferguson and Klotz. The constants C were derived by means of Eq. 1 from the API filter losses of the muds used by the authors (t = 1,800 sec; A = 45.16cm2). A three-cone bit was used (n = 3) at 90 rpm (m = 1.5). The calculated figures are compared with the experimental data in the table below. The calculated values of Q, are usually lower than the experimental values. This may be due to the following causes. 1. The value of C used in the calculation is based on the API filter test (filtration pressure of 100 psi), whereas the experimental data were obtained with a filtration pressure of 200 psi. Although the effect of the pressure on C is not large, C decreases somewhat with increasing pressure, and this leads to a higher filtration rate. 2. Mud losses and the eroding action of the mud stream on the cake are not entirely negligible. 3. The values of Q, derived by Ferguson and Klotz from their experiments are too high, because of their assumption that all pore liquid within the formation drilled is picked up by the drilling mud. It is found, however, that the calculated values of Qf, except in the case of oil base muds, are of the right order of magnitude. ACKNOWLEDGMENT The author wishes to thank the management of the Koninklijke/Shell-Laboratorium, Amsterdam, for permission to publish this note.

Jan 1, 1957

By P. Schwarzkopf, J. H. Brophy

A modification of the Mendenhall wedge blackbody1 has been used to determine solidus temperatures and to anneal alloys in the tantalum-rhenium binary system. The technique has proven to be simple and accurate with modest power requirements. For temperatures up to 2800° C a piece of 10-mil tantalum sheet was folded double and formed as shown in Fig. 1. The middle of the resulting ribbon filament was a cylindrical-shaped crucible with less than a 1/8-in. opening. After inserting a specimen in the cavity, the filament was clamped between molybdenum electrodes in a high vacuum chamber. A representative filament 2 in. long and % in. deep was heated to 2800°C with a current of 700 amp at 4 v. The specimen temperature was determined by sighting into the cavity with a Leeds and Northrup optical pyrometer. The twisted filament shape was necessary to avoid serious geometric changes during thermal expansion. For temperatures between 2800" and 3000°C a 4-mil tungsten filament was employed. To facilitate fabrication it was warm-folded, and a twisted segment of 10-mil tantalum was used to support one end to absorb thermal expansion. This element assembly required about 700 amp at 10 v to reach 3000°C. Two geometric modifications of the filament were helpful for solidus temperature determinations. A shallow chamber, with depth to opening ratio of 3 to 1, permitted direct observation of the specimen through the optical pyrometer. The fact that the specimen was visible permitted the melting point to be determined when sharp features on the specimen surface became rounded; it also indicated that blackbody conditions did not prevail. By standardizing against the melting point of molybdenum, the observed melting temperature was corrected by the following form of Wien's Law: in which T is the true temperature, To is the observed temperature, and K is a constant characteristic of the filament geometry and determined experimentally for the molybdenum standard. The resulting corrected melting point for each alloy served as a reference temperature for the second more precise filament geometry. With a 6 to 1 depth to opening ratio, the specimen was indistinguishable from the filament interior, indicating good blackbody conditions. Using this technique, a series of specimens was isothermally treated at temperatures above and below the corrected direct reading. Incipient melting was detected by visual or micrographic examination of the specimen after cooling. This procedure was checked with specimens of pure chromium, molybdenum, and tantalum. Table I represents the values obtained, together with the solidus temperatures in the tantalum-rhenium binary system determined by the same technique. The alloy specimens were approximately 1/8 in. in diam. They were pieces of 10-g buttons melted four times in a nonconsumable tungsten electrode arc furnace on a water cooled copper hearth in 2/3 atmos of titanium gettered helium. Several sources of error are possible in such temperature measurements. Within the accuracy of the pyrometer no gradients were detectable near the specimen, and element distortion was virtually eliminated by twisting the tantalum. Compensation was made for the 1/8-in. sight glass by inserting several identical thicknesses and extrapolating to zero thickness. As a result an additional 10°C correction was added to all observations in the temperature range of 2500" to 3000°C. The principal source of error was then in the operation of the

Jan 1, 1961

By P. E. Baker

Approximate solutions are presented for the heat-flow equations in a loss-free linear system with a moving source and with heat transfer by convection and conduction, representing in situ combustion in an oil reservoir. The rate of heat generation and the velocity vf of the source (flame front) are assumed constant. A cold front or convection front caused by the cooling effect of in-jected air develops behind the flame front and moves with velocity vc, which is determined by the thermal properties of the air and rock. Because of thermal conduction the fronts are not sharp; i.e., they do not represent temperature discontinuities. The following solutions apply after a sufficiently long time. where Q is heat generated per unit volume of formation, k is thermal conductivity, CF is volumetric heat capacity, a is thermal diffusivity, and subscripts 1 and 2 refer to values behind and ahead of the flame front, respectively. The parameter CF2 is contained in v . Te is initial reservoir temper- . C2 e ature and air-injection temperature. Other mathematically possible solutions are presented. The different solutions result from the use of different values for various physical parameters. The solution just presented is thought to be most commonly applicable. INTRODUCTION In this paper, approximate analytical expressions are derived for the temperature profile developed in the underground combustion method of oil recovery. A qualitative description of the process may be found in a paper by Tadema.1 The flame front is regarded as a moving source with a constant rate of heat generation. Heat transfer is by conduction and convection. Previous publications, of which a few are cited here, 2-5 have also attacked this problem and have presented solutions pertaining to different methods of approximating or idealizing the process studied. The present paper also treats an idealized case: linear flow is assumed for heat and fluids, and vaporization and condensation effects are neglected. The results obtained are similar to those derived by Bailey and Larkin,3 but are obtained by an entirely different procedure. The method used here should give considerably greater insight into the physics of the in situ combustion process. Four types of cases are considered, distinguished by thermal and fluid-flow properties of the system. A constant rate of heat generation and constant rate of flame-front advance are assumed. Flame-front temperature is determined for each case using a heat balance which involves the entire temperature profile. The applicability of the different solutions to real systems is discussed after they are all presented. Again, this is done for the purpose of understanding better the physics of the process. Consideration of the nonapplicable solutions and of the reasons for their not applying is significant. In a paper by Cooperman,4 the only case solved is one considered here as not applicable. Fluid flow, as such (pressures, saturations, oil recovery, etc.), is not treated. This subject has been covered in a paper by Wilson, et al.6 Also, we are not concerned with requirements for continuance of the process; we only attempt to determine the temperature history for cases where the process has continued for some time. PHYSICAL SYSTEM AND APPROACH TO PROBLEM A linear flow (heat and fluid) system is assumed and the x-axis is taken parallel to the flow direction. The combustion zone (flame front) is vertical,

By Nick Holonyak

Halogen vapor-transport synthesis of Ga(As,-,Px) and its preparation into laser junctions are described. Electrical and optical properties of Ga(As,-,PX) laser junctions are discussed. The present limitations in these properties are related to material proble?vzs and the very early state of development of Ga(As,-,PX), and are discussed in this context. Inhonzogeneity problems, fluctuation of As :P ratio, and problems with deep-level contaminants are described and related to Ga(As,-,PX) junction performance. Laser junctions are demonstrated which operate to wavelengths as short as 6470 A (77°K). The prospect that Ga(As,-,P,) will operate to wavelengths perhaps 100A shorter is mentioned. IN this paper we wish to describe some of the more important features of almost 1 year of experience in the preparation and properties of Ga(As,-,P,) p-n junction lasers. Because much data so far available are far from complete, some of the results still must be considered tentative and subject to correction and revision as work on Ga(As,-,P,) crystal problems progresses. Although the electrical, optical, and device properties of Ga(As,-,P,) junction lasers are understandably of considerable interest, the work to date points out that by far the most serious problems extant and those deserving first attention are problems involving the growth, doping, and perfection of Ga(As,-,P,) crystals. One of the most formidable of these is to grow Ga(As,-,P,) sufficiently free of deep levels, either due to contaminants or to structural imperfections, to allow fabrication of laser p-n junctions which can be cooled and not suffer from "freeze-out" of carriers on deep levels (and consequent double-injection behavior). In addition to the problems of growing crystals adequately free of deep levels and generally of the highest perfection, so that the best possible laser junctions can be realized, the further goal remains of increasing the phosphorus content well beyond 40 pct in an attempt to determine the practical lower wavelength limits of laser action in the Ga(As,-,P,) system. Even though the laser junctions prepared in Ga(As,-,P,) are of importance in their own right, we have considered them at this point mainly a means to study the growth and crystal problems of the material. It can be concluded that the laser junctions now available are almost completely limited by the purity and structural deficiencies of Ga(As,-,P,) crystals, and cannot be fairly compared with, for example, GaAs p-n junction lasers until Ga(As,-,P,) crystal growth has been more extensively developed. The basis for the statements above will become evident in the following sections which describe Ga(As,-,P,) crystal and junction preparation, and laser-junction properties. G(As,-,P,) CRYSTAL GROWTH As previously reported,2 we have found it convenient to employ the halogen vapor-transport process3 for synthesizing Ga(As,-,P,) crystals for use in laser junctions. Commercially available GaAs and Gap, separately prepared by halogen vapor tranport, are sealed in the desired ratio in a quartz vessel with a quantity of column-VI donor and a small quantity of metal halide which supplies the halogen for transport. The sealed ampoule, as shown in Fig. 1, is heated at a temperature in the range from 1025" to 1100°C at the position of the source GaAs and Gap. The GaAs and Gap are simultaneously vapor-transported and deposited as Ga(As,-,P,) at one end of the ampoule

Jan 1, 1964

By W. A. Stickney, J. W. Town

Tests demonstrated that aqueous solutions of sodiu~n sulfide would dissolve over 95 pct of the cinnabal- in 5 pct Hg flrotation concentrates and 60 to 90 pct of the cinnabav in low-grade ol-es. Double-leach tests showed that potassiutn sulfide would dissolve 90 pct of the avsenic sulfide in Hg-As satnples and only 1 to 10 pct of the Hg; the sodium sulfide would then dissolve 80 to 90 pct of the rernaining Hg and 30 to 70 pct of the vemaining As. 1 HIS paper describes the extraction, by alkaline sulfide solutions, of mercury from cinnabar-bear ing ores and flotation concentrates. Leaching time and solution temperature had minor effects on mercury extraction when compared to the effects of reagent quantity and ore type and grade. Cinnabar, although readily soluble in sodium sulfide, was only partially soluble in potassium sulfide and essentially insoluble in ammonium sulfide. A double leach process was developed to extract selectively the arsenic from Hg-As products with K2S and to treat the residue with sodium sulfide-hydroxide solutions to extract the mercury.' Mercury was then recovered from the pregnant solutions either by precipitation with metallic aluminum or by electrodeposition. The solubility of HgS in alkaline sulfide solutions was first reported by Volhard in 1878.' The first reported commercial application was made in 1915 when Thornhill applied the method to the treatment of an amalgamation tailing.3 Mullhollen, in 1911. described the chemical reaction of HgS with Na,S and alkaline hydrate to be:4 Most investigators have reported using a 4-pct sodium sulfide and a 1-pct sodium hydroxide soluti~n.3-4 An increase in temperature or excessive dilution of the solution causes the reaction to be reversed. Church Holmes described a similar process used for the extraction of antimony from silver concentrates at the Sunshine Mining Company's mill at Kellogg. Idaho.5 More recently. Erspamer and Wells reported the results of leaching studies on a Hg-Sb ore from Alaska.6 EXPERIMENTAL PROCEDURE Leaching tests were made on samples of mercury ore from eight deposits in Oregon, Washington, and Idaho. In addition. tests were made on flotation concentrates from seven of the samples as well as a flotation concentrate from an operating mill. Since previous investigators reported reagent requirements greatly in excess of that required by the equation HgS + Na2S = HgS . Na2S, initial studies were made on chemically pure HgS. Results showed that the reaction actually required about 1 g of Na,S per g of HgS in an aqueous solution rather than 0.338 g of Na,S as indicated by the equation. To check further the matter of reagent requirements, Na2S and HgS were mixed together in equal mole ratios. Water was then added, a drop at a time, until the components reacted; X-ray diffraction analyses showed no HgS nor Na,S present. The yellow hydrate compound which formed would not redissolve until about three additional mole equivalents of Na,S were added to the solution. This indicated that a stable solution would require at least 4 moles of Na2S for each mole of HgS. While these implications may be valid for pure HgS, the possibility of entirely different results caused by the existence of other elements present in ores and concentrates was recognized. Consequently, experiments of the same order were made on samples of a flotation concentrate from a producing mill. The concentrate, containing about 18 pct

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