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By K. K. Kelley

Sodium-aluminum and potassium-aluminum silicates are among the more important rock-forming minerals of the earth's crust. They also appear as constituents of some metallurgical slags and of some refractory materials. Consequently, knowledge of their thermodynamic properties is interesting and valuable from several viewpoints. This paper reports experimental determinations of the low-temperature heat capacities and entropies at 298.16° K. of albite, jadeite, and nephelite it the sodium-aluminum silicate series and of adularia, ferriferous orthoclase, leucite and kaliophilite in the potassium-aluminum silicate series. Also high-temperature heat-content and entropy increments about 298.16° K. are reported for albite, jadeite, nephelite, and carnegieite in the sodium-aluminum silicate series. Except for a few high-temperature heat-content values for albite, all these data are available for the first time.

Jan 1, 1953

By W. J. Fene

The lowest number of fatalities from coal-mine explosions in the United States in any year since records have been kept was the total of 8 in 1949 and again in 1950. Even incomplete records as far back as 1870 reveal a larger annual loss of life from explosions. From 1890 to 1948 the lowest annual loss was 32 in 1946. A smaller total of 15 fatalities was reported in 1952. Figure 1 shows the total yearly loss of life from explosions in all coal mines since 1880. Those in anthracite mines alone are shown by the shaded area. The erratic variation of the chart line shows the difficulties that have confronted the industry in the struggle to control and eliminate mine explosions. Potential hazards have existed in marry mines without realization that only a small change in conditions could initiate a disaster. Many disasters causing great loss of life occurred in mines that had been regularly operated without incident for long periods. Although the number of coal-mine explosions causing great lose of life has been kept down in recent years, the exceptions still make the record anything but satis¬factory. There have been almost no widespread explosions for several years, but in a few instances many lives were lost from afterdamp. Although the violence and spread of mine explosions may be controlled, the loss of life may be heavy if many of the men happen to be in the path of the smoke and gases. For these reasons, the strictest controls must be maintained to eliminate all factors that might combine to cause even a small ignition of gas or dust.

Jan 1, 1953

By Jack Washburn, E. R. Parker

Kinking in zinc single-crystal tension specimens was observed under conditions of low stress and high temperature. Kinking is discussed in relation to other plastic bending phenomena on the basis of dislocation theory. Experiments on the stress-induced motion of small angle boundaries are reported. KINKING was first reported by Orowan1 as a new deformation mechanism. He observed the phenomenon in cadmium single crystals loaded in compression. Glide lamellae in a local region of the rod were observed to snap over suddenly to a tilted position, resulting in a sudden shortening of the specimen. Between the tilted portion and the rest of the crystal there were fairly sharp boundaries, with the slip plane assuming approximately mirror image positions on opposite sides of these boundaries. Orowan considered the boundaries to be regions where dislocations had concentrated. Hess and Barrett' observed the formation of kinks in critically oriented zinc compression specimens. It was found that the sudden snapping over of the tilted region was not an essential part of the kinking phenomenon but rather was associated with the method of loading. Kinking was explained on the basis of the accepted mechanisms of slip and flexural glide. It was also suggested that a kink can be considered as a special type of deformation band. During a recent investigation of the effect of surface condition on creep of zinc single crystals," a similar phenomenon was observed in crystals which were loaded in tension. The specimens were 0.4 in. diam cylindrical rods with a free length of 4 in. between end connections. All of the crystals were tested at a constant load. adjusted to give an extension rate of approximately 0.05 pct per hr. Kinking, as shown in Fig. 1, occurred in some of the tests performed at temperatures above 200°C. Kinking was observed in specimens varying widely in initial orientation, scattering about a 45" angle between the slip plane and the specimen axis. The condition leading to kinking in tension appeared to be non-uniform distribution of flow along the gage length combined with the restraint imposed by the tensile load. At low temperatures and fast strain rates, the distribution of strain throughout the midsection of tension specimens was generally quite uniform; therefore, bend planes developed only near the ends as described by Miller.4 However, at high temperatures under creep conditions it was difficult to obtain specimens in which the distribution of flow was uniform. Some of the factors which may have caused differences in flow stress along the length of the crystals are: Nonuniform distribution of impurities, accidents of growth (lineage structure), slight bending or other damage during handling, surface conditions, and strain-aging characteristics due to dissolved nitrogen." Plastic flow, once started in a local region, often continued to a relatively large strain before other parts of the gage length became active. Under these conditions a series of kinks, such as those in Fig. 1, were produced. Fig. 2 illustrates how a nonuniform distribution of slip produces bending moments which- are responsible for kink formation. If no plastic bending were to occur while the rod extended by pure slip in two separate sections of the rod, it would assume a shape such as that in Fig. 2a. A specimen having this shape and being subjected to a tension load would have concentrations of stress at the concave surfaces C and lower than average stress would exist at the convex surfaces D. Therefore a bending moment is superimposed on the average stress in the regions between C and D. The positions of potential bend planes under these conditions are shown as dotted lines. Actually no such shape as Fig. 2a develops because plastic bending in the region C-D occurs simultaneously with pure slip in the intervening regions. The observed structure of a tension kink is indicated by Fig. 2b. Perhaps the best approach to an understanding of kinking as well as other related plastic bending phenomena, such as the bend planes discussed by Miller,' cell formation studied by Wood et al.,6 and polygonization,7 is consideration of the dislocation model of a bent lattice. Current theories of the slip process postulate generation or multiplication of dislocations at certain lattice imperfections. The mechanism proposed by Frank and Read8 results in continuous generation of concentric dislocation loops which spread out

Jan 1, 1953

By J. P. Newell, R. W. Storey

This paper describes the development of a continuous float-and-sink process to produce coal low enough in ash content to be suitable for production of electrodes. The cleaned coal had a combined iron and silicon content of 0.239 pct. The efficiency of recovery was 84 pct. AUGER mining is a form of continuous mining in that it completely replaces with a one-cycle operation the older conventional cut, drill, shoot, and load method of mining. Relatively new, having been utilized only within the last few years, it is even more continuous in its production of coal than some other forms of continuous mining being practiced in this country today. There are at present coal recovery augers in operation working along strip-mined highwalls from the outside. This paper will deal with underground mining, specifically with an experiment which was carried out with a machine developed for this purpose. The location of this experiment was in Pike County in eastern Kentucky in the upper split of the No. 3 Elkhorn seam. Coal height was 32 in. and roof conditions were very bad, with 10 in. of soft draw slate coming down with every cut in conventional mining. The coal is high-grade bituminous, excellent for metallurgical coking. Underground auger mining fills a need for a method of recovering coal in thin seams, under bad roof conditions or in split seams. In many cases it might save money by eliminating the handling of excessive quantities of rock. In fact, if the coal can be recovered, as in the case of this experiment, without mixing with any impurities outside the seam, it may be possible to load or ship a satisfactory product with little or no preparation or cleaning expense. The need for some economical method for recovering coal from thin seams is becoming more pressing as the more profitably mined seams are exhausted. Basic Principles of Auger Mining The principles of the auger, or screw conveyor, have long been used in drilling small diameter holes for blasting and other purposes. These same fundamentals apply to large diameter drilling. However, considerably more attention was given to designing a cutting head that would not pulverize the coal and consequently would require a minimum of power to drive it. The head, as designed for this job, consists of a cylinder 25 in. in diam with steel bits set in 3 positions spaced around the forward rim. A conventional coal drill bit, at the head of a bursting cone in the center of the cylinder, trails the forward rim slightly, see Fig. 1. The bursting cone and auger connections are anchored to the cutter barrel by 3 arms spaced at 120". This head design proved to be very satis-

Jan 1, 1953

The equipment and general smelter layout for the Mount Isa Copper Smelter were designed by engineers associated with the American Smelting and Refining Company and by Mount Isa staff engineers. The final notice of site was dictated by the need for 'building the smelter near the existing Mount Isa power house to enable full use to be made of the steam from the waste heat boilers. Although much excavation work was necessary before concrete foundations could be poured, the location lends itself to further expansion should it become necessary. The plant is designed and constructed to involve straight line smelting operations which include the following major steps in the overall scheme.1. Charge make-up.2. Roasthig.3. Reverberatory smelting.4. Converting.5. Refining.6. Casting.CHARGE MAKE-UPA system of proportioning bins is provided for preparing the feed mixture for the roasters, Sulphide concentrate containing 24% copper wiil be delivered by belt conveyor from the filter plant to the smelter storage patio. This is a large roofed concrete floor that provides a maximum storage capacity of 8,000 tons of concentrate. Eight proportioning bins located below but adjacent to the south end of the patio will be used for actual charge make-up from which concentrate, ore and flux will be proportioned to the feed belt and conveyed to the roaster feed hoppers. Four of the proportioning bins, 80 tons capacity each, will receive...

Jan 1, 1953

By F. D. Rosi, C. A. Dube, B. H. Alexander

WHEN a deformed polpcrystalline metal is heated to a sufficiently high temperature, a recrystallized structure develops which consists of small, essentially stress-free grains. This transformation is referred to as primary recrystallization. Under certain conditions, on prolonged annealing of the specimens, a type of grain coarsening occurs in which a small number of grains commence to grow at various points by devouring the neighboring finegrained primary structure, which, in itself, exhibits a marked stability toward normal grain growth. This grain coarsening process has been referred to by Burgers' as "secondary recrystallization" or "exaggerated grain growth." Although much work has been done on recrystallization and growth processes, present knowledge of the factors which determine the occurrence and growth of secondary grains is inadequate for the advancement of a theory which accounts for the observed characteristics of this recrystallization phenomenon. In this respect, it would be important to make measurements of the velocity of growth of these large secondary grains. The early work of Feitnecht2 on aluminum showed that the size of secondary grains increased with temperature and time, suggesting that such measurements would be possible. More recently, Burgers1 found that the growth velocity of these grains in aluminum was constant over a large time interval, as is generally found for the growth velocity of primary grains in a uniformly deformed test piece.3-5 It is reasonable to expect that the determination of the activation energy of the secondary growth process might lead to a better understanding of the underlying atomic mechanism. This investigation, therefore, is one of a series primarily designed to measure the growth velocity of secondary grains at various temperatures for silver, copper, and aluminum. It is hoped that these studies along with those of orientation relationships, will establish a sound basis for theorizing as to the origin and nature of the secondary transformation. Experimental Procedure The metal used in the present investigation was high-purity silver (999.9 fine), which was supplied in the form of cold-rolled plates 0.250 in. thick. These plates were annealed at 500°C for 1 hr and then straight-rolled to a thickness of 0.04 in. in three reductions of approximately 45 pct, followed in each case by an anneal at 450°C for 1/2 hr. The 0.04 in. sheets were given a final reduction of approximately 50 pct, which resulted in a thickness of 0.02 in., thereby insuring two-dimensional crystal growth. Individual specimens of this material about 1x3 cm were used for all heat treatments, unless otherwise noted. The annealing was carried out under an atmosphere of argon in an Inconel tube furnace whose temperature was controlled to within -+2°C. Metallographic examination of the secondary transformation was accomplished by mechanically polishing the specimens on one side to approximately one half their thickness through 2/0 metallographic emery paper, and then electrolytically polishing in a solution of potassium ferrocyanide and sodium cyanide. With a current density of approximately 20 amp per sq dm, the time required to obtain a satisfactory surface varied from 3 to 5 min. Standard potassium bichromate was used to etch the electrolytically polished surfaces. A heavy etch with this solution produced a sharp contrast between the secondary grains and the fine-grained primary structure, darkening the latter while leaving the large secondary grains bright. All area measurements of the secondary crystals were made with a planimeter on enlarged tracings of the grains.

Jan 1, 1953

By C. S. Lord

"AbstractThe slow progress of conventional geological reconnaissance of the northern Canadian Shield during the past twenty years clearly indicates the need for a radically new field technique. Operation Keewatin, involving the use of helicopters as the traversing vehicles, was planned and executed by the Geological Survey of Canada in response to this requirement.About 57,000 square miles of District of Keewatin, N.W.T., were mapped during the 1952 field season in appropriate detail for publication at 1 inch to 8 miles. The Operation disclosed about 14,100 square miles of Precambrian sedimentary and volcanic rocks ranging in •age from Archaean to Late Proterozoic. About 7,700 square miles of this area are underlain by greenstone. This work was accomplished in a field season of 113 days, including the spring break-up. Routine aerial geological observations were made from two helicopters flying about 300 feet above the ground; these observations were checked by more than 1,700 landings and about an equal number of aerial observations from heights of less than 50 feet. Logistical support was •provided by a Norseman aircraft on skiis or floats. Combined helicopter and Norseman flying time was about 990 hours. More than 1-00 square miles were mapped per helicopter-hour, and about 815 square miles were examined each day that both helicopters operated. The reconnaissance cost about $207,000, or $3.63 per square mile mapped.As a result of this trial use of helicopters there is now available a reasonably proven method whereby an acceptable geological reconnaissance of the barren grounds of the Canadian .Shield within the Districts of Keewatin and Mackenzie might be completed within a decade. Thus, within a few years, it could place at the disposal of the prospecting and mining fraternity data which, by conventional methods, might not be made available to this generation. Due weight must be accorded this time factor when evaluating the aerial technique."

Jan 1, 1953

By W. M. Peirce, E. A. Anderson

A FEW metals have been known since the dawn of history. Many have been prepared in quantity only within the present century. Zinc falls into an intermediate category, although there is some evidence of its existence in elemental form in Greece as early as the third or fourth century B.C. Nevertheless, the first important use of zinc antedates the earliest records of civilization. This first use was in the alloy, brass, which is roughly one third zinc. This continues to the present time as one of the major uses of the metal. The first production of brass, in light of present knowledge, was perhaps one of the 'most romantic and fortuitous of technical discoveries. Copper, the major constituent of brass, had been given to man by Nature in the native state; that is, as lumps of fairly pure copper. The art of melting and working it had been learned. But zinc does not occur as the metal in Nature and even if some early metallurgist happened to heat zinc ore with a reducing agent, the reduced metallic zinc passed off as vapor and was lost. Doubtless some early coppersmith, melting copper in accidental contact with zinc ore, reduced the zinc, and the vapor was absorbed by the molten copper. Its color, hardness, and other properties were thus wonder- fully changed. And so the earliest metallic form of zinc, as nearly as we can deduce, existed in the alloy brass. Probably knowledge of the kind of rock with which to heat copper to change it to brass, the best

Jan 1, 1953

By J. B. Macelwane

Historically whenever application of scientific results to a new problem required the special experimental background, the economic outlook and the practical knowledge characteristic of the engineer, a curriculum in that type of engineering based on the professional requirement grew up in the engineering colleges. This is precisely what is happening now in geophysical engineering. THE Mineral Industry Education Division of AIME has long been interested in geophysical education. Organized in 1938, a Committee on Geophysical Education presented a number of reports in succeeding years. The AIME is an engineering society; hence it might be expected that the interest of the Mineral Industry Education Division would have centered about the relation of courses in geophysics to engineering education. However, this was not the case. The burden of the discussion held under the auspices of the Committee on Geophysical Education bore on geophysics in general and particularly on its relation to geology. In the decade that has passed since those meetings much water has flowed under the bridge. Not only have the geophysical sciences developed at an extraordinarily rapid rate but the practical importance and the range of their applications have spread in ever widening circles and have even assumed a very prominent place in research programs of the military, the Army, the Navy and, particularly, the Geophysical Research Directorate of the Air Force at Cambridge, Mass. So enormously have the geophysical sciences as such grown in scope and in degree of specialization that no one man in a lifetime of study can hope to master the theoretical and experimental complexities or even to follow intelligently in the published literature all the varied accomplishments of basic research in these fields. As in the other sciences, most of the results of geophysical research have potential economic value and are being applied to a wider and wider range of human needs. Here we see a parallel with the older sciences and their relation to engineering. Whenever the applications of scientific results required the special experimental background, the economic outlook, and the practical knowledge characteristic of the engineer, a curriculum in that type of engineering grew up in the colleges and universities. In the words of the "Report of the Committee on Adequacy and Standards of Engineering Education" in the January 1952 number of the Journal of Engineering Education: "Engineering education in America was not developed after a preconceived plan. It evolved in parallel with the needs of a growing country, a country engaged in the development of a vast industrialization. From the first it filled a practical need, and its design emanated largely from an evaluation of the professional requirement." The advent of the railroad created a need for scientifically trained engineers and the response was the curriculum in civil engineering. The development of steam power created the demand for a curriculum in mechanical engineering. Neither of these types of engineers was trained to cope with the requirements of electrical power, and so there came to be a curriculum in electrical engineering. The advent of radio communication and of electronics during the first World War and in the years that followed resulted in the establishment of electronics engineering, sometimes within the curriculum in electrical engineering and sometimes independent of it. The complexities of industrial management have created an ever increasing demand for industrial engineers and the consequent building up of a curriculum in industrial engineering. The wide industrial application of chemical processes required a type of engineer whose background was training in chemistry but who was able to design processes and plants on an industrial scale; hence we have the curriculum in chemical engineering. The advent of the airplane created an entirely new set of problems which were solved by the training of aeronautical engineers. Many of these have called for more and more science and mathematics. Such was the history of the older engineer-

Jan 1, 1953

By A. L. Engel

[This report describes preliminary tests of samples from six deposits of oxidized copper ores .in Nevada. The tests for the most part were confined to laboratory-scale acid leaching to extract the copper.'The exceptions consisted of flotation tests to demons' ate the possibilities of treating the ore by that method. The samples tested were representative of oxidized copper ores from six counties in all parts of Nevada. The results obtained by the preliminary tests described were indicative of the extractions of copper to be expected, In the five leaching experiments, the approximate consumption of acid was also indicated.]

Jan 1, 1953

By Jean Herenguel

THE published work of Lacombe and Beaujard' has demonstrated the interesting application of etch figures to the determination of crystal orientations in aluminum by a purely micrographic method. The geometry of these figures leaves no ambiguity and the method has the added advantage of being applicable to very small crystal units. These authors applied the technique to the study of high purity aluminum, and it has now been adopted buy Heren-guel and his collaborators to various researches on commercial aluminum, containing up to 1 pct Fe and Si. This must modify the opinion point,ed out by

Jan 1, 1953

By R. C. Buehl, M. B. Royer

High manganese slags of low phosphorus and iron content are produced by air oxidation of high phosphorus spiegeleisen in a basic-lined converter. Control of phosphorus and iron within specification limits for ferromanganese ore feed is obtained by a unique cyclic operating procedure. Various types of slags, or synthetic manganese ore, can be made. AN affiliated paper' describes the production of high phosphorus spiegeleisen containing 14 to 23 pct Mn and up to 4 pct P in an experimental blast furnace from open-hearth slag or manganiferous iron ore. This phosphorus content is too high for use of the spiegel in normal steel-production operations. Consequently, a preferential separation must be effected whereby the manganese is concentrated in a product that is usable in industrial operations. The preferential separation methods being investigated for this phase of the work are confined to pyrometal-lurgical processes for ready incorporation into steel-plant operations. It is fortunate that manganese is more actively oxidizable than iron or phosphorus, and therein lies a preferential separation method for isolating manganese from these two elements. Silicon is more strongly oxidizable than manganese, and its oxidation precedes, or occurs simultaneously, with manganese. Therefore, manganese and silicon are separable into a high manganese oxide slag phase while the phosphorus and iron remain in the molten metallic state. Complete separation of these elements represents an ideal condition which is not generally attainable in actual operations. This pyro-metallurgical method for separating manganese from phosphorus and iron by preferential oxidation was investigated by blowing 500 lb of metal in a basic-lined vessel to obtain preliminary information on the effectiveness of the procedure. Certain conditions of attainment in the separation process are desirable in any method for removing manganese from high phosphorus spiegeleisen, such as: 1—High recovery of manganese in the oxidation product; 2—the product to be of equal or better quality than ferromanganese-grade ore—48 pct Mn minimum, less than 10 pct SiO2, and Mn-P ratio of 300:1; and 3—attainment of the enumerated objectives in a product amenable to industrial handling, such as a slag of high manganese content that will flow from the processing vessel and of sufficient fluidity for ready separation of metallic granules that may have become mixed with the manganese slag phase. Previous Work Recovery of manganese from low grade ores and industrial byproduct slags by smelting to spiegeleisen, with subsequent oxidation to synthetic ferro-manganese-feed ores, has been a subject for periodic investigation during the past four or five decades in the United States and Germany. Joseph' and associates of the Bureau of Mines North Central Experiment Station, Minneapolis, Minn., smelted manganiferous iron ores of the Cuyuna range, Minn., to spiegeleisen and subsequently tried air and ore oxidation procedures for concentrating the manganese into synthetic ferrograde manganese ore. Joseph's results on the operation of a side-blown basic-lined converter for air oxidation of manganese from molten spiegeleisen were so discouraging that the procedure was abandoned after 11 blowing tests. Much slag was thrown from the converter vessel; phosphorus content was four to five times the maximum allowable for ferro ore; and a manganese-iron ratio of only 2 or 3:1 was obtained in the slag instead of the required 8:1. Oxidation of manganese from spiegeleisen with about 0.5 pct P, by adding iron ore to molten spiegel in an experimental open-hearth furnace, proved moderately successful in Joseph's experiments. The main drawback to the operation was the necessity for over-oreing for effective oxidation of the manganese with consequent too high iron oxide residual in the slag. Furthermore, the phosphorus content was proportional to the iron concentration and therefore much too high, so that several hours of reduction by a carbonaceous material were required to adjust the iron and phosphorus to the desired content of high grade ferro feed. A troublesome feature of the slag product of the spiegel oxidation process was its lack of fluidity if the silica content was less than 10 pct, the concentration considered desirable for the synthetic ore. Approximately twice the desired concentration of silica was required to impart enough fluidity for transfer from the vessel by pouring. The acute shortage of manganese in Germany

Jan 1, 1953

By Eric Kula, Åke Josefsson

L. J. Dijkstra and R. Sladek, (Ontario Research Foundation, Toronto, and Institute for the Study of Metals, Chicago, respectively)—This interesting paper confirms some results obtained some years ago in collaboration with Fast: namely the broadening of the nitrogen peak by the presence of small amounts of manganese. Later on a more extensive study of this effect was made at the Institute for the Study of Metals at Chicago. As the work has not yet been submitted for publication we wish to mention here briefly some of the results. The effect of about 0.5 atomic pct manganese, chromium, molybdenum, or vanadium on the nitrogen-peak in iron was examined. The broadening found previously in the case of manganese was even found to be more pronounced for chromium. In the case of molybdenum and vanadium a double peak was observed which seemed to justify the idea that in all cases mainly two relaxation times were involved: namely, the normal relaxation time as found in pure iron and a second relaxation time related to the existence of abnormal interstitial lattice sites introduced by the foreign metallic element. The analysis showed that for the normal nitrogen-peak as a reference at 22°C the abnormal peak was found at about 32°, 47°, 75°, and 87°C in the case of manganese, chromium, molybdenum, and vanadium, respestively. In the manganese alloy the free energy difference for a nitrogen-atom at an abnormal and a normal lattice site was estimated at 2800 cal per mol. This means that for temperatures above 100°C the solid solubility and overall diffusion rate of nitrogen is not much affected by additions of 0.5 pct Mn. We believe that the difference in rate of precipitation of nitrogen in pure iron and the manganese alloy is mainly a question of the number of potential nuclei available in the different steels. In studying the effect of these alloying elements on precipitation of nitrogen, a distinction must be made between the para reaction and ortho reaction, using terminology introduced by Hultgren.7 The ortho reaction in which the alloying metallic element participates in the diffusion under formation of nitrides occurs at high temperatures such as 600°C. The para reaction in which the alloying metallic element does not diffuse and in which the nitride inherits its alloy content from the matrix occurs at lower temperatures. To prevent the ortho reaction the alloys have to be quenched rapidly from the phase. It is not surprising that the authors find that the height of the peak indicates a lower nitrogen content than chemical analysis. In the first place the peak is not a single relaxation peak and secondly, the steels were not quenched from the phase after the nitrogen was introduced at 580 °C.

Jan 1, 1953

By W. G. Pfann

The simultaneous segregation of two solutes during the directional solidification of an ingot is treated mathematically on the basis of simplifying assumptions. Expressions are derived for the difference in concentration of two solutes, and for the location and concentration gradient of a pn barrier formed in a semiconductor by the segregation of a donor and an acceptor. THE problem of normal segregation of a single solute during the freezing of an alloy has been treated mathematically by a number of investigators. Gulliver' showed that coring increases the quantity of eutectic above that to be expected at equilibrium, for a system having limited solid solubility and, on the basis of simplifying assumptions, calculated the fraction of eutectic to be expected. Scheuer2 expressed composition of solid solution in terms of a distribution coefficient and the fraction solidified and compared experiment with calculation for the systems A1-Cu, Al-Zn, Cu-Sn, Cu-Zn. Hayes and Chipman,3 in a detailed study of segregation in a low carbon, rimming steel ingot, calculated distribution coefficients for a number of solutes in iron, compared calculated and experimental segregation curves, and discussed the effects of process variables such as rate of solidification and stirring. In the present paper a mathematical analysis is made of the simultaneous segregation of two solutes during the orderly freezing of a solid solution system, with particular emphasis on the difference in solute concentrations. Although the analysis is quite general and can be applied to the segregation of minor elements in alloys, it is directed in particular at the solidification of a semiconductor containing a donor and an acceptor. Normal segregation has unique aspects in a semiconductor, because of the ways in which donors and acceptors affect the electrical properties. The difference between two solute concentrations becomes of importance, as does also the gradient of the difference where the difference goes through zero, this being the concentration gradient of excess carriers at a pn barrier. A primary object of this paper is to extend the mathematical treatment of segregation to include these newer aspects which are of particular significance for semiconductors. One property of interest is the electrical conduc- tivity, which arises from the presence of donors 'or acceptors in solid solution. The conductivity may be either n-type or p-type depending on whether donors or acceptors, respectively, are in atomic excess. For both germanium and silicon, elements of Group V of the Periodic System, such as P, As, and Sb, are donors and elements of Group 111, as B, Al, In, and Ga, are acceptors.4-6 If a donor or acceptor is present alone in solid solution, the conductivity is proportional to its concentration." If both a donor and an acceptor are present, then the conductivity is proportional to the difference in their atomic concentrations. If the donor and acceptor segregate at different rates then a pn barrier in certain circumstances may form at some point in the ingot. Accordingly, equations are derived and illustrated which express the effect of segregation on: 1—the concentration of a single solute with a discussion of the assumptions; 2—the difference between two solute concentrations and means for minimizing its variation in an ingot; and 3—the location and concentration gradient of a pn barrier. The analysis is applicable to processes in which the entire charge is melted and then progressively frozen from one end. The method in which an ingot is solidified in a crucible7 and that in which a solidifying rod is pulled from the melt8 both fall into this category. Segregation of One Solute If a cylinder of molten alloy is caused to freeze slowly from one end, a normal segregation of solutes will usually occur, producing a lengthwise concentration gradient in the ingot. Depending on whether a solute raises or lowers the melting point of the solvent, it will become concentrated in the first or last regions, respectively, to freeze. If it is assumed that freezing is such that there is no diffusion of solute in the solid, complete diffusion in the liquid, and that k, the distribution coefficient, defined as the ratio of solute concentration in the just-freezing solid to that in the liquid, is constant, then the

Jan 1, 1953

By Edwin B. Cook

This report presents the results of calculations of the equilibrium composition of the products of combustion with air of six different mixtures of octane CgH18, plus PbEt4 and halogen-bearing scavengers at three air-fuel ratios, at pressures of 5 and 30 atm., and at temperatures of 350°, 1,000°, 1,800°, and 2,000° K. The air-fuel weight ratio has the values 12, 15:12, and 18. The concentration of PbEt4, M, in milliliters per gallon of iso-octane, has the value 1 or 3. The word "case" is used to designate the halogen concentration. Three cases have been considered [ ]

Jan 1, 1953

By J. G. Kirby

According to the annual Bureau of Mines survey of refinery capacity, there were 343 petroleum refineries in the United States as of January 1, 1953, with a total daily crude-oil throughput capacity of 7,638,661 barrels. Compared with the previous year, this represents a decline of 7 in the total number of refineries, but a gain of 305,776 barrels in daily crude-oil throughput capacity. The capacity of the average refinery to process crude oil increased to 22,270 barrels, a gain of 1,319 barrels during 1952. All refining districts reported increases in installed capacity for the year, with Texas Gulf Coast accounting for 28 percent of the increase; California, 21 percent; and the Indiana-Illinois-Kentucky district, 18 percent. Additional crude-oil capacity under construction January 1, 1953, was 60 percent greater than at the beginning of 1952. The total reported, 509,721 barrels daily, is a record high for refinery expansion. In addition to the new facilities under way, facilities for 127,755 barrels daily are being installed to replace those that are obsolete. Four new refineries were under construction at the beginning of the year, and three of these are now in operation. Plans for five' new refineries have been announced, but actual construction has not been started.

Jan 1, 1953

By David Swan

No mystery shrouds the discovery of chromium. The indefatigable French chemist Vauquelin, in reporting his discovery of this chemical element to 1'Institut National in 1798, concluded his discourse with the statement: "I place before the eyes of the Institute a small quantity of chromium and several of its most re- markable combinations." Working with the so-called "red lead of Siberia, Vauquelin not only prepared numerous chemical compounds of the new metal, but he reduced the oxide to the metallic state. These chemical compounds possessed a variety of remarkably distinctive colors; so, acceding to suggestion, Vauquelin named the new element chrome (chromium), a derivative of the Greek word chroma, meaning color. Siberian "red lead" (crocoite) was not plentiful; however, it was not long before Vauquelin's prediction was realized that the chemical compounds of chromium would become useful in the arts when sources of chromium became more readily available. Although chrome-iron ore (chromite) became obtainable in France, the United States and elsewhere during the early part of the nineteenth century, it is interesting to note that from 1828 to about 1860, Maryland, Pennsylvania, and others of the eastern United States furnished almost the entire chrome-ore requirements of the world. Several countries each in turn have since dominated for certain periods the supply of chromite. In recent years, the largest tonnages have come

Jan 1, 1953

By W. T. Turrall, D. Porter

The paper describes a machine developed for the purpose of concentrating clear optical grade fluorspar crystal from a feed material containing less than 1 pct impurities. The principle of concentration is based on the fact that in a liquid having an index of refraction equal to that of fluorite (n — 1.434) clear crystals are invisible, whereas crystals containing occluded impurities absorb a part of the light. As the crystals pass through a light beam, undesired crystals give themselves away by creating a shadow on a photoelectric receiver. .The shadow is converted by the photoelectric cell into an electric pulse. An electronic circuit amplifies this pulse and commands the operation of a mechanical concentrator. Hp HE crystal laboratory, Dept. of Physics, Massa--*- chusetts lnstitute of Technology, was confronted with the problem of obtaining a supply of optical grade calcium fluoride (CaF,) for use in growing synthetic CaF, crystals. A search of the known fluorspar deposits did not indicate that any quantity of optical spar could be obtained. Even the best material had to be sorted by hand to remove impurities. The process for growing CaF, crystals developed by Professor D. C. Stockbarger of the Dept. of Physics, M.I.T., necessitates very pure feed materials. Exclusion of impurities is required, even in amounts detectable only spectrographically. The impurities occurred as minute inclusions of SiO,, BaSO,, CaCO,, FeS2, water or air. Crystals up to 4 in. in diam and weighing several pounds are made by the Harshaw Chemical Co. in Cleveland. Since the time required to grow a 4-in. crystal is about one week, and since the cost of manufacture is high, removal of impurities by any concentration method appeared practical. The mineral engineering section of the Dept. of Metallurgy undertook to investigate the possibility of concentrating clear optical fluorspar, —4 mesh + 10 mesh, from a feed containing over 99 pct CaF,. Various innovations of the known methods of concentration were considered, but in each case the minute amount of impurities associated with the crystal produced such extremely small differences

Jan 1, 1953

By G. W. P. Rengstorff, R. B. Fischer

A study was made of the effect of impurities on the bend ductility of cast molybdenum. High purity molybdenum was repared by re-melting under high vacuum. The ductility of "transverse-grain" specimens indicated that intergranular brittleness decreased with an increase in purity of the metal. THE production of as-cast molybdenum with high ductility at room temperature would make working of the metal easier and increase the usefulness of the as-cast metal. Furthermore, a .knowledge of the factors that influence the ductility of as-cast molybdenum might be applied to the problem of making fusion weldments having satisfactory room-temperature ductility. Individual grains of commercial as-cast molybdenum are slightly ductile at room temperature. However, the presence of carbides at the grain boundaries may cause the metal to fracture in a brittle manner. This behavior has been discussed.' The amount and distribution of the impurities in as-cast molybdenum would be expected, from previous research on the metal, to have considerable influence on its ductility. Some effects of oxygen and carbon on the mechanical behavior of the metal were discussed by Parke and Ham,2 Woodside,3 and Zappfe. Landgraf, and Worden.4 Parke and Ham2 found that, if a sufficient number of molybdenum oxide particles were present at the grain boundaries, the intergranular cohesion was reduced to the extent that arc-melted molybdenum would rupture intergranularly during hot forging. They also found that if the oxygen content was less than 0.003 pct, the cast molybdenum was hot forgeable. It is suspected, however, that forgeable molybdenum may contain a small amount of oxide that could reduce the ductility of the as-cast metal at room temperature. Also, there is the possibility of the unfavorable distribution of other impurities having a detrimental effect on the ductility of cast molybdenum. The results of a study of the influence of purity on the room-temperature ductility of cast molybdenum are presented here. Vacuum Arc-Melting to Produce High Purity Mo One way of determining the effect of impurities on the ductility of molybdenum is to prepare and test metal as free of all impurities as possible. Accordingly, the present investigation was undertaken with this in view. Arc melting in high vacuum (less than 0.1 micron of mercury) was chosen as the method for reducing the impurities below the concentrations occurring in commercial molybdenum. Commercial arc melting of molybdenum is carried out at about 50 microns pressure. During the arc melting, carbon and oxygen in the metal react to form carbon monoxide. By virtue of the vacuum process, the partial pressure of carbon monoxide is maintained at such a low value that the reaction greatly lowers oxygen and carbon contents. An excess of at least 0.03 pct C is used in commercial arc melting to insure that the oxygen content will be below 0.003 pct. The excess carbon remaining after the deoxidation step forms carbides on freezing. Some of the carbides precipitate at the grain boundaries and, as will be shown, have an unfavorable effect on the room-temperature ductility. In the present work, only the small amount of carbon (0.003 pct) contained in the commercial powder-metallurgy molybdenum used for melting stock was present. Partial removal of oxygen from the melt probably occurred as the result of the volatilization of molybdenum oxides, or by distillation of oxygen at the high melting tem-

Jan 1, 1953

By L. A. Rapoport, W. J. Leas

The original Burkley-Leverett theory has been extended and a more detailed formulation of the waterflood behavior in linear horizontal systems is presented. Particular consideration has been given to the evaluation of capillary pressure effects and differential equations permitting an explicit evaluation of these effects have been derived. On the basis of the developed theory it is recognized that the flooding behavior is dependent upon the length of the system and the rate of injection. At the same time it has been determined that systems of different lengths yield the same flooding behavior if the injection rates and or the fluid viscosities are properly adjrrsted or "scaled." It has also been found that the sensitivity of the flooding behavior with respect to rate and length decreases as any one of these {actors increases in value and that for sufficiently long systems and high rate.; of water injection the flooding behavior becomes independent of rate and length. or "stabilized." To such stabilized conditions the theory formulated by Buckley and Leverett is applicable. A number of laboratory flooding tests have been made and good agreement Iraq been found between theory and experimental observations. The experimental results are discussed and it is shown that under field conditions the flooding behavior is usually stabilized. As a result of these finding; a procedure is indicated for evaluating field performances either on the basis of tests performed with commonly available core samples or by means of calculations using relative permeability data INTRODUCTION In recent years the development of methods for evaluating oil recovery by waterflooding has been the object of considerable research. A theoretical analysis of the mechanisms involved in the displacement of immiscible fluids was originally established by Buckle!- and Leverettl and experimental investipatio~~s have been made by numerons workers." Many of the experimental results are in mutual agreement and bear out several significant features of the flooding mechanism as predicted by theory. Thus it lias been generally recognized that a flood corresponds to the movement of a steep saturation hank or "front" (primary phase), followed by additional gradual oil displacement (subordinate phase). It has also been found that for any porous medium the flooding behavior is largely dependent upon the oil-water viscosity ratio and that for increasing values of this ratio the relative importance of the primary displacement phase decreases while that of the subordinate phase becomes more pronounced. Although the studies to date have clarified certain aspects of the flooding process. they have given rise to observations of a somewhat contradictory nature that cannot he explained in terms of the original theory. These observations pertain mainly to the effect of injection rate or pressure gradient upon recovery. Some investigators report laboratory tests that indicate incresing oil recoverieq with increasing rates of water injectill, others find the flooding behavior to be independent of and other. mention lower oil recoveries with increased injection rates.3 The conflicting evidence indicated above creates considerable uncertainty with respect to laboratory testing procedures and the utilization of the resulting data for field evaluations. The principal purpose of this paper, then, is to resolve these Uncertainties by means of a comprehensive theoretical and experimental investigation of the flooding meanism. THEORETICAL DEVELOPMENT Derivation of Flooding Equations The mathematical description of transient flow phenomena is based upon the consideration of the various processes occurring during an infinitesimal time interval in an infinitesimal volume element and upon the correlation of these processes with those occurring in the adjacent elements. The volume elements are defined as being infinitesimal in comparison to the overall dimensions of the porous system, yet each sufficiently large so aS to encompass the full range of pore openings encountered throughout the system. If a porous system can arbitrarily be subdivided into an infinite number of volume elements all possessing the same distribution of pore openings and if this distribution is unformly continuous. the system may be said to be homogeneous. Such a homogeneous porous medium is considered in the present studivs. It is furthermore postulatecl that only oil and water are present in the pornu wediu. that they act a- totally incompressible and immiscible fluids. and that gravity effects are negligible. In n linear flow system of unit cross sertional area. as treated here. the infinitesimal volume element.; to he considered are cylindrical ".slices" of thickness dx. oriented perpendicularly to the direction of flow. The equations applicable to any such volume element. at my time. describe the movement. of oil and water across the element:

Jan 1, 1953