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By W. F. Kieschnick, Eugene Harrison, W. J. McGuire

W. J. McGuire, et al, are to be commended for their undertaking of a mathematical solution of a very difficult problem. Unfortunately, however, a mathematical approach requires the application of several assumptions. These assumptions appear to be unrealistic and lead to answers which do not describe what actually happens when hydraulically fracturing oil and gas wells. Considering laboratory confirmation of breakdown phenomena, the authors appear to have tested their theories only on cement specimens and on samples of Austin limestone, much too small to provide any fracture system. This work resulted in the formation of vertical fractures. If the authors had tried similar experiments on thick walled cylinders made from almost any sandstone cores, they would have found that, using crude oil as the breakdown fluid, horizontal fractures would almost always occur, and at pressures much lower than any calculated. They would also find that by confining the fluid to within the bore (using oil base mud for example) on similar samples, the pressures required to burst the cylinders would be considerably higher and most of the fractures would be vertical. This breakdown pressure behavior has been duplicated in wells in Texas, Oklahoma, Kansas and in Wyoming. Considering field data the phenomena of different breakdown pressures for different breakdown techniques can be further illustrated. Most production and service personnel will agree that a breakdown can be more easily obtained if injection into a formation can be established prior to the occurrence of the breakdown. This is true whether the formation being treated is completed as open hole or as a perforated interval. This is clearly illustrated by a Lakota well in Wyoming, completed open hole at a total depth of 7,358 ft. An attempt to vertically fracture this well failed when a bottom hole pressure of 10,326 psi was insufficient to break down the formation. A non-penetrating type fluid (oil base mud) was in the well at the time the breakdown was tried." The oil base mud was then cleaned out of the well and replaced by a 30" API gravity crude oil. With this oil in the hole the formation breakdown was easily accomplished at a bottom hole pressure of 3,607 psi. This large difference in fracture pressures would be impossible according to the theories presented by McGuire, et al. The authors have used as an example the breakdown pressures experienced when acidizing Permian Basin wells. During acid treatments of limestone and dolomite the "breakdown" (drop-off in pressure) seldom occurs until some injection of acid has been accomplished. In these cases the breakdown is most likely to result from the chemical reaction of acid and rock in already existing vugs and fractures rather than from making a new fracture by hydraulic pressure. If this is true, then results in the Permian basin should not be used to validate the authors' calculations. *** AUTHORS' REPLY to ROSCOE C. CLARK and HENRY F. COFFER The purpose of our laboratory experiments in which thick-walled rock cylinders were hydraulically fractured was to determine the validity of the "thick pipe" formula for brittle materials, and not to predict nor demonstrate directly the orientation of field fractures. Our conclusions concerning field results resulted from calculations involving the "thick pipe" relationship as well as considerations of overburden stresses, rock strengths, and the geometry and dimensions of the field system. Clark suggests that had the models been more porous or contained weak bedding planes, horizontal fracturing would have occurred. This is undoubtedly true provided external stresses similar to those in the earth's crust are nor imposed. However, if we were going to design experiments to represent directly the field case we would impose the proper stresses on the models. It is generally recognized that the vertical compressive stress in the earth's crust arising from the weight of the overburden is approximately 1 psi/ft of depth. Then, as an example, even though a horizontal bedding plane has zero strength, the formation cannot be separated to form a horizontal fracture unless the hydraulic pressure exceeds the stress due to overburden. And in those cases in which the stress resisting vertical fracturing is significantly less than that resisting horizontal fracturing, vertical fractures should result, notwithstanding horizontal plane weaknesses. We agree that breakdown pressure will be less if the fracturing fluid penetrates the formation. In Appendix HI of our paper it is shown that leak-off reduces the pressure necessary to initiate either a horizontal or vertical fracture. It would be difficult to attempt to

Jan 1, 1955

By N. S. Stoloff, K. R. Jordan

The temperatwe and grain size dependence of the mechanical avoperties of ordered and disordered Fe-49 pct Co-2 Pct V were investigated. The yield and flow stresses obeyed the Hall-Petch relationship u = ai + kd-&apos;I2. Ohdering reduced the intercept stress cjj and raised the Petch slope, k, at all temperatures. Ordering also increased the temperatwe dependence of k. The ductile to brittle transition temperature increased with order and grair~ size. Cleavage fracture was nucleation limited and the fracture stress did not zlary linearly with d-&apos;". A quantitative test of the Cottrell-Petch fracture theory (and recent modifications which consider the influence of slip mode), demonstvated that this theory is not applicable to FeCo-V. COTTRELL&apos; and etch&apos; independently suggested that a criterion for cleavage failure at the yield point, a,, based on dislocation pileups at a grain boundary or other obstacle to dislocat.ion motion, is: aYYkd&apos;I2 1 opy [ll or, equivalently, aikz,d112 +k:)bpy [2] where a, and ky are the Hall-Petch intercept and slope, respectively, 2d is the grain diameter, P is a geometric factor dependent on the macroscopic ratio between shear and tensile stress, p is the shear modulus, and y is the true elastic surface energy. When the product of quantities on the left side of the equation is equal to or exceeds that on the right, cracks should be able to nucleate and propagate at the yield stress, as shown schematically in Fig. 1. Therefore a high intercept stress, high Petch slope, or coarse grain size favors brittleness. petch3 associated the existence of a ductile to brittle transition in ferrous alloys with the temperature dependence of ai. One of the earliest modifications of the Cottrell-Petch theory was presented by ~rmstrong,~ who derived an expression for transition temperature in terms of several measurable flow and fracture parameters. The latter paper was able to rationalize situations in which the transition temperature increases with decl-easing grain size, as in the case of molybdenum,&apos; and also suggested that Ppy should be a function of grain size as well as temperature. More recently Johnston et a1.6 and Smith and worthington7 have suggested that the temperature or composition dependence ol&apos; ky must also be taken into account if there is any cha.nge in deformation mode, as from wavy to planar slip, or wavy slip to twinning, with change in temperature or solute content. Armstrong %as suggested that for hcp metals changes in o;k,dw> o;k,d1/2< / is / ^^^^ / / y_______________________________________ d-"2 Fig. l—Schematic representation of grain size dependence of yield stress, cry, and fracture stress, CTF. Intersection defined by Cottrell-Petch equation. slip mode should be incorporated in the theory through changes in the critical resolved shear stress for the slip system which controls ky. The purpose of the present investigation was to critically test the modified677 Cottrell-Petch theory of fracture in the superlattice alloy Fe-49 pct Co-2 pct V, by studying the grain size dependence of the yield and fracture stresses over a range of temperatures, in conjunction with an investigation of slip mode and fracture behavior. Previous work has shown that long range order results in a sharp decrease in flow stress, a small increase in work hardening rate and a drastic upward shift in the ductile-brittle transition temperature of F~CO-V.~&apos;~ The only comprehensive study of slip character in this alloy has been reported in a preliminary account of the present investigation.10 EXPERIMENTAL PROCEDURE The experimental work was carried out on material produced from a 10 lb vacuum melted ingot, of composition 49.32 wt pct Co, 2.09 wt pct V, balance Fe. 30-mil thick sheet samples with a 1; in. gage section were machined from cold rolled stock. The degree of cold work ranged from 85 pct for the finest grained samples to 5 pct for the coarsest grain size. Details of ingot fabrication are reported elsewhere." Equi-axed grain sizes in the range 12.7 to 75.4 p were obtained by annealing for varying times at 850°C. (Re-crystallization annealing time, rather than temperature , was varied to control grain size to insure that samples of all grain sizes contained equivalent quenched-in vacancy and interstitial concentrations.) Grain sizes were measured by the line intercept method on several specimens of each grain size. Following recrystallization, all samples were disordered by quenching into iced brine.

Jan 1, 1970

By J. Alfred Berger, O. M. Katz

Selected samples of hydrided Zr-Hf alloys were rapidly quenched to voom temperature and exrtrnined metallographically, by X-ray diffraction, and through micro hardness studies to confirm high-temperutuve data Confirming experiments sllowed that there were five phases in this Lernary system: 1) hextrgonal with lattice parameters similar to that of the initia1 Zr-Hf alloy but slightly enlarged due to dissolved hydrogen; 2) fee with properties of a brittle, intermediate, hydride compound; 3) fct with c/a crvoltnd 1.07 and which appeared as a neetilelike precipitale; 4) hexagonal, designated ?, with c/a ratio of 2.37; and 5) orthorhombic, designated X, with a = 4.67, b = 4.49, and c = 5.093 and whose tnicro-st?ruct~ival nppetrl-nnce depcncled o/i, heat lvecrt~r~ent. The tetragonrrl phase never crppeal-erl witkorct the cubic hydricle. Abpecrrtrnce of 0 and A also tlependet on the hafnium content of the zirconium. A previous paper&apos; on the Zr-Hf-H system described the thermochemical data obtained with a high-vacuum, high-sensitivity mirrogravimetric apparatus. This data presented a fairly complete picture of the phase relationships at elevated temperatures. However, it could not establish the actual crystal structures, lattice parameters, or metallographic disposition of the hydride phases. The present complementary study utilizes X-ray powder patterns along with light and electron microscopy to characterize completely the five hydrided phases found in Zr-Hf-H alloys quenched to room temperature. Crystallographic features of the zr-Hf,2,4 zr-H,5-7 and Hf-H8 systems have been summarized in Table I. Designations of a, ß, and ? were retained in the Zr-Hf-H system for the phase regions through which the pressure-composition isotherms always sloped. However, it was not firmly agreed that these were single-phase regions.&apos; In fact, the region designated y always contained a cubic as well as a tetragonal phase after quenching to -196°C. MATERIALS Preparation of the high-purity Zr-Hf alloys has been described.&apos; The four zirconium alloys which were hydrided contained 37 wt pct Hf (23 at. pct), 51 wt pct Hf (37 at. pct), 73 wt pct Hf (58 at. pct), and 91 wt pct Hf (82 at. pct), respectively. These were designated B-2, B-4, B-6, and B-8. Photomicrographs of the initial alloys showed the material to be quite clean as would be expected from the precautions exercised in producing them. However, there were a number of annealing twins but no other subgrain structure. In addition to the four original alloys, fifteen hydrided samples were observed at room temperature. Hydrogen compositions are given at the top of Tables I1 to V. APPARATUS The phases present at elevated temperatures were studied by quenching hydrided samples to room temperature by two different methods, both under vacuum: 1) fast cooling of the sample tubes of the microgravimetric apparatus1&apos;9 with flowing air and 2) rapid quenching into liquid nitrogen. The cooling rate for 1) was 750° to 250°C in 30 sec. Since the microbalance chamber was not designed to permit very rapid cooling of a hydride sample, all liquid-nitrogen quenching was done in an auxiliary experiment. The auxiliary quenching apparatus consisted of a small-bore, high-temperature furnace, a sealed SiO2 tube containing the sample, and a dewar quenching flask filled with liquid nitrogen. The hydrided sample, previously quenched in the microgravimetric reaction chamber, was placed in a platinum boat in a vacuum-degassed SiO2 tube. A zirconium wire getter and degassed SiO2 rod, to reduce the internal volume, were also in the tube. After sealing the tube under vacuum the zirconium getter was heated to absorb the last traces of gas. Only the sample was heated at the reaction temperature for the desired length of time, and then the tube dropped through the opposite end of the furnace into the dewar. A quenching rate of 200" to 400° C per sec was estimated. Analyses of samples after the auxiliary experiment also showed practically no increase in oxygen or nitrogen content from heating in the SiO2 tube. All of the samples were examined at room temperature by the X-ray powder method. The majority of the powder patterns were obtained with double nickel-filtered CuKa radiation after 8- and 16-hr exposures in an 11.48-cm-diam camera. Cobalt and chromium radiation were also used to spread out the high d value end of the Pattern. Such patterns readily identified the minor phases. NO oxide or nitride lines were found. Where sharp back-reflection lines existed it was possible to reduce the

Jan 1, 1965

By F. S. Norcross

MANGANESE has long been considered one of the United States&apos; most important strategic raw materials. Its indispensability in steel manufacture makes it vital to the nation&apos;s industrial life. Coupled with this indispensability is the fact that domestic producers have not been able as yet to supply more than a small part of the nation&apos;s manganese needs; consequently the United States has had to depend upon such distant foreign sources as the U.S.S.R., British India, the African Gold Coast and Brazil for the major portion of its ore. The great bulk of the mineral is consumed in the form of ferromanganese, an alloy that averages 8o per cent manganese and 20 per cent mainly iron and carbon. Manganese is used as a deoxidizer and desulphurizer in steel manufacture. By combination with the residual oxygen and sulphur of the bath, it helps to produce a clean, sound metal. Approximately 14 lb. of manganese, it is estimated, is used in making one ton of steel. For standard-grade ferromanganese, the ore should have a minimum of about 48 per cent Mn and preferably more. Beneficiation methods have not yet been developed for making the immense low-grade deposits in the United States salable at prevailing prices. Dependence upon foreign sources thrust the United States into serious difficulties during the World War. At the start of hostilities in 1914, the nation was obtaining about four-fifths of its ore from the Eastern Hemisphere. Domestic production had been negligible, amounting to only 3000 to 7000 tons a year. As the war continued, shipments from the East, endangered by sea attack and blockade, dwindled rapidly. Imports from Brazil mounted. In this grave emergency, the United States, starting almost from scratch and under the stimulus of high prices, succeeded by 1918 in producing a peak of 311,000 tons, about 3 5 per cent of its consumption that year. Since the war, the United States has depended upon foreign sources for more than nine-tenths of its high-grade ore. During 1936, 1937 and 1938, imports for consumption averaged 736,000 tons a year. During the same period, domestic shipments averaged 21,000 tons a year. Of the imports, the U.S.S.R. accounted for an annual average of 280,000 tons, the Gold Coast 208,000 tons, India 74,000 tons, and Brazil 72,500 tons. But India and Brazil, which in 1936 ranked third and fourth in the list of importers, were displaced in 1937 and 1938 by a new and much nearer source-Cuba. From less than 1 per cent of United States imports in 1931, the island republic increased its shipments to more than 27 per cent in 1938. Cuba&apos;s average for this three-year period was 97,000 tons, and its total for 1938 was 131,000 tons.

Jan 1, 1940

By Shiou-Chuan Sun

THE presence of an excessive amount of tough froth in the flotation of minerals, particularly coals, may create trouble in dewatering, filtering, and handling. Froth is also a nuisance in many chemical industries.&apos; This paper presents a study on the destruction of extremely tough froths with intense high-frequency sound. The data indicate that sound waves can be employed for continuous atandsoundwavescan instantaneous defrothing. A powerful high-frequency siren was used in obtaining the data. Also tested was an ultrasonorator of the crystal type with a frequency range of 400, 700, 1000, and 1500 kc per sec and a maximum power output from its amplifier of 198 w. The results, not presented, indicate that as now designed this machine is not suitable for defrothing. Although the sound generators of the magnetostriction type2,3 and of the electromagnetic type&apos;.&apos; were not available, it is beelectromagneticlieved they are capable of producing the required sound intensity for defrothing. The use of ultrasonics for defrothing was suggested by Ross and McBain1 in 1944. Ramsey8 reported in 1948 that E. H. Rose mentioned a supersonic device that broke down flotation froth but with low capacity. The writer has not been able to find any published literature containing practical experiments. Theoretical Considerations The mechanism of defrothing by sound is attributed to the periodically collapsing force of the propagated sound waves and the induced resonant vibration of the bubbles. The collapse of froth is further facilitated by the sonic wind and the heat of the siren. Sound waves can exert a radiation pressure&apos;," against any obstacle upon which they impinge. When a froth surface is subjected to the periodic puncturing of sound waves, the bubbles are broken. According to Rayleigh9 and Bergmann,12 the radiation pressure of sound, P, in dynes per sq cm is given as: P = 1/2 (r+1)i/v where r is the ratio of the specific heats of the medium through which sound is traveling and is equal to 1 on the basis of Boyle&apos;s law; i is the sound intensity in ergs per sec per sq cm, and v is the sound velocity in cm per sec. In this case, the accuracy of the formula is only approximate, because a perfect reflection can hardly result from a column of froth. In addition to the radiation pressure, the propagated sound waves cause the bubbles of the froth to have a resonant vibration.&apos;" he vibratory motion of the bubbles causes collision and coalescence, thereby weakening if not breaking the bubble walls. Sonic wind and heat were also generated." The sonic wind can exert pressure on the froth surface, and the heat can evaporate the moisture content of the bubble walls as well as expand the enclosed air. Apparatus The defrothing apparatus, shown in Figs. 1 and 2, consists of a powerful high-frequency siren, a glass or stainless steel beaker of 2-liter capacity with 12.4 cm diam and 17.1 cm height, and a metal reflector. The beaker was placed 2 in. above the top point of the siren. The metal reflector was adjusted to reflect and focus the generated sound waves into the central part of the beaker. Fig. 2 shows the crystal probe microphone used to measure the acoustic intensity and the mandler bacteriological filter employed to introduce compressed air into the beaker for frothing. The apparatus was enclosed in a soundproof cabinet equipped with a glass window. The siren, shown in Fig. 3, consists of a rotor that interrupts the flow of air through the orifices in a stator. The rotor, a 6-in. diam disk with 100 equally spaced slots, is driven by a 2/3 hp, Dumore W2 motor at 133 rps. The frequency of the siren can be varied from 3 to 34 kc. The maximum chamber pressure is about 2 atm, yielding acoustic outputs of approximately 2 kw at an efficiency of about 20 pct. The siren itself is relatively small and can be operated in any orientation. A detailed description of the siren has been given by Allen and Rudnick.11 Collapse of Froth To study the sequence of the collapse of froth, the glass beaker was partially filled with 920 cc water, 100 g of —150 mesh bituminous coal, 0.3 cc petroleum light oil, 0.2 cc pine oil and 1.54 cc Pyrene foam compound. This mineral pulp was agitated for 5 min and then aerated through a mandler filter until the empty space of the beaker, approximately 9 cm high, was filled completely with min-

Jan 1, 1952

By B. F. Zwick

No new fields have been discovered in Ecuador during 1945, though Shell. Company of Ecuador&apos;s Vuano No. 1, near Arajuno in the Oriente concession, which was reported to have drilled to .5281 ft., tested a small, noncommercial quantity of 13° gravity oil. In the upper section, the well tested large flows of fresh water and has been abandoned. Shell is preparing to move to another location.

Jan 1, 1946

By Hugh H. Waesche

Of all the military services, the Signal Corps is the most concerned with piezoelectric minerals because of its function as a supply service to the strategic and tactical military forces. Consequently this paper is written from the point of view of one associated with that organization. The Signal Corps is responsible for the research, development, and supply of communications, radar, and components to the using services of the Department of the Army and to some extent the Other branches of the National Defense Department. Their work therefore includes the study of the sources* characteristics, and application of quartz and other piezoelectric materials. These materials have become a vital consideration in strategic planning and are essential for efficient tactical operation by all the Armed Forces. The Signal Corps at the beginning of world War 11 Was respon-sible for both Army Ground and Air Force electronic equipment. Since that time this Army service organization has probably done more in the development of frequency control devices using piezoelectric materials than any other group. The U.S. Department of the Interior, Bureau of Mines, Minerals yearbook of 1945, shows that during the four war years, 1942 through 1945, 9,598,-410 Ib of quartz crystal were imported for all uses and of this total, 5,168,000 lb were consumed to produce 78,320,-000 crystal units for electronic application. Other government records confirm these data which conclusively show that approximately 53 pct of the crystalline quartz imported was consumed in the production of electronically applied quartz crystal units. It may be assumed that some effort was made to maintain a stockpile over demands for all purposes. and this would mean that the actual percentage of quartz used electronically was considerably over the 53 pct figure. These data only emphasize that electronic application of crystalline quartz was the greatest requirement, and per- haps the actual value in this application to national defense is many times greater in importance than is apparent on first inspection. Current electronic research and development programs of the Armed Forces are planned around the fundamental use of piezoelectric minerals for frequency control and this at present, at least, means quartz. Definition and Early Development The word piezoelectricity is formed from combination of the Greek word "piezein". meaning "to press," and "electricity." It is that property shown by numerous crystalline substances whereby electrical charges of equal and opposite value are produced on certain surfaces when the crystal is subjected to mechanical stress. It appears to be intimately associated with the better known property, pyro-electricity and in fact, the two may be manifestations of the same phenomeuon. This property was discovered by Pierre and Jacques Curie in quartz, tourmaline, and other minerals in 1880 while studying the symmetry of crystals. The converse effect, that is, mechanical strain in the crystal when placed in an electrical field, was predicted by the French physicist, G. Lippman, in 1881, and verified by the Curies almost immediately. As has been the case with many discoveries of similar character in the basic sciences, not much attention was paid to this property for man)- years except as an entertaining curiosity. Between 1890 and 1892 a series of papers was published by W. voigt in which the theoretical physical properties were put into mathematical form. The first practical application of piezoelectricity occurred during World War I when professor P. Langevin of France used quartz mosaics to produce underwater sound waves. The same mosaics were used to pick up the sound reflections from submerged objects which were in turn, amplified by electronic means and used to determine the distances to such objects. This device was intended for use as a submarine detector but development was not completed in time for war service although it was used later for determining ocean depths. About the same time, A. M. Nicholson, of Bell Telephone Laboratories, developed microphones and phonograph pickups using Rochelle salt crystals. A major step in the application of piezoelectric quartz came in 1921, when professor W. G. Cady, of wesleyan university, showed that a radio oscillator could be controlled by a quartz crystal; from that date, this use of quartz has increased steadily, reaching its peak in world war 11 as is shown by the figures previously given. Essentially all American electronic equipment for communication, navigation, and radar, utilized quartz crystals for the exacting frequency control required. Crystalline Minerals with piezoelectric Properties QUARTZ Hundreds of piezoelectric crystalline materials are known, most of which are water soluble. Of these, quartz appears to be without a peer for electronic frequency control. Unfortunately, the quartz must be of superior quality. It must be free of mechanical flaws, essen-tially optically clear, free of both Brazil and Dauphiné twinning and must be, for average uses, over 100 g in weight. Because of these stringent requirements, raw quartz of the quality desired is of rare occurrence. In addition to quartz, several other naturally occurring crystalline materials are known to have the piezoelectric property and could perhaps be substituted for quartz in some applications. These

Jan 1, 1950

By A. E. Bellis

There is a wide difference of opinion among rifle experts in the matter of barrel steel, and the relative importance to the life of the barrel of the steel&apos;s composition, heat treatment, structure, and physical properties. In order to promote discussion, which it is hoped may&apos; lead to the discovery of the source of some of the traditional beliefs on the subject, the results of some tests are presented here, with data on heat treating, physical tests, and erosion. The detailed metallographic study of this steel is given in another paper.l The conclusions from these tests should be capable of wider application than their direct bearing on the barrel-steel problem. The Government specifications for barrel steel for model 1903 rifle (Springfield) call for carbon 0.50 to 0.60 per cent., manganese 1.00 to 1.29 per cent., silicon under 0.25 per cent., sulfur under 0.06 per cent., phosphorus under 0.08 per cent. The minimum physical requirements are: Tensile strength, 110,000 lb. per sq. in. (7733 kg. per sq. cm.); yield point, 75,000 lb. per sq. in (5472 kg. per sq. cm.); elongation, 20 per cent.; reduction of area, 45 per cent. Material fulfilling these requirements gives practically no failures when proof-fired, with charge of 70,000 lb. per sq. in. pressure, which is 40 per cent. in excess of the service charge. The turning and drilling operations show up any seams or laps such as accidentally occur even in the best heats of open-hearth steel, so that faulty stock is practically all eliminated before proof-firing. These physical requirements are met either by rolling billets at a proper temperature down to the form of tapered barrel blanks or by heat treating bars that have been upset to cnlarge the breech section. The transformation temperature of this steel, on heating, is around 1350" F. (732&apos; C.), varying somewhat with the composition and the rate of heating. The actual treatment of the barrel blanks, as carried out by different manufacturers, gives four kinds of barrels, which will be called A, B, C, and D, for convenience. A barrels result from heat treating upset blanks by quenching at

Jan 1, 1920

By C. E. Stafford

and tougher, and will carry double the tonnage of any of Dr. Dud ley&apos;s soft mils. C. E. Stafford, Steelton, Pa.: I must confess my high ap preciation of Dr. Dadlq&apos;s conscientious and painstaking work, and of his scientific methds in obtaining the data; but with his method of handling these results and with his conclusions drawn therefrom 1 canuot agree. The reasons for this difference of opinion I will endeavor to explain. It is apparent on inspecting his Plates 6 and 7 that the majority of the slower-wearing rails are from the north track, and generally have a longer time of service, a greater average tonnage per rail, and a smaller avernge tonnage per year per rail than the faster wearing, the majority of which are from the south track, and gener ally have a shorter time of service, a smaller average tonnage per rail, and a greater average tonnage per year per rail. Have these facts any significance Have these different of conditions to which they are subjected any baring on the relative wearing capacity of these rails I venture to say they have. I think, after a study of Table I (page 676), (an arrangement of linee 17 and 18 of Plate a), in connection with Plates 6 and 7, we will find that the slower wear of the 32 best rails is only partly due to qualities inherent in the rails themselves, but is principally due to external conditions favorable to slower wear. In regard to the north and south track, we know that over the rsoiith track come the loaded cam from the West, and that over the north track these cars return, most of them, empty. It is evident that this means for the north track a less average tonirage per rail per year; or, in other words, a lower wheel tonnage. When the load per wheel is less, the resistance and consequently the wear must, necessarily, be less, other things being equal. Time of service, alee, has an important bearing on the question in hand. It has been only within the last five or six years, as Dr. Dudley has pointed out, that the roadbed of the Pennsylvania Rail road has reached its present admirable condition. Before this time the njadbrd was more elastic, more yielding (and probably not uni tbrmly so) than at present. These circumstalices might cause a sofier rail to be more durable than a harder one, owing to the fact that it ulonId yield rnore or less to the bending force of the passing load and would thus get a bearing on each cross-tie. The harder rail, on the other hatid, being stiffer and more. unyielding, would not

Jan 1, 1881

By D. Mills, G. B. Craig

ZIRCONIUM has been float-zone-refined in an electron-beam furnace and the redistribution of oxygen, iron, and tungsten has been measured. The iodide zirconium used in the present experiments initially contained both oxygen and iron in the range 100 to 200 ppm by weight, and tungsten in amounts less than 10 ppm. Float-zone refining of zirconium, using induction heating, has previously been attempted by Kneip and Betterton1 and Langeron.2 Kneip and Betterton were primarily interested in the removal of iron and nickel. They achieved some purification, with respect to both these elements, in material given up to six passes at 150 mm per hr under an argon atmosphere. Langeron reported purification for a large number of elements after four completed passes in a static vacuum system operating at pressures less than 10-6 mm of Hg and with rates of zone travel between 30 and 40 mm per hr. He did not report oxygen concentrations, but stated that there was inverse segregation of this element. westlake5 has also used a minimum of four zone passes to remove iron from zirconium. No rates or conditions were given. Belk6 has shown that tungsten contamination can occur during electron-beam melting. He reported an increase from 0.01 to 0.05 pct by weight tungsten in molybdenum after four complete zone passes. The vacuum system for the electron-beam unit used in the present investigation consisted of a single-stage rotary pump backing a liquid-air-trapped oil-diffusion pump. A pressure of less than 10-8 mm of Hg was obtained with Dow-Corning 705 fluid in the diffusion pump. In order to avoid contamination of the zirconium by evaporation from the tungsten filament, a special focusing cage4 was employed. Three rates of zone travel, 114, 38, and 4 mm per hr, were investigated, with the liquid zone moving from the bottom to the top of the bar. The bars used were 3 mm diam and the total melted length was 130 mm. Oxygen was analyzed by neutron-activation analysis using a neutron flux of 10&apos; neutrons per sq cm per sec to form the isotope N16 by the 016 (n,p) N16 reaction. The standard deviation is quoted for each oxygen determination. The iron and tungsten analyses were performed spectrographically, and the precision is estimated to be ±6 pct. Analyses for tungsten were all below the detectable limit of 10 ppm, confirming the protection given by the focusing cage. No significant redistribution of oxygen was found at the two higher rates of zone travel. The redistribution of oxygen and iron obtained after five passes at a rate of zone travel of 4 mm per hr (1.1 x 10-4 cm per sec) is recorded in Tables I and 11. Burris, Stockman, and Dillon3 have estimated the distribution of solutes during multipass zone refining. Using their curves for an effective distribution coefficient of Keff = 1.5 and 2 for oxygen and Keff = 0.3 for iron, the expected concentrations were estimated for the present material. These are shown in Tables I and 11, along with the experimentally measured values. The calculated concentrations are based on a molten-zone length of 10 pct of the total melted length, whereas in the present experiments the molten zone was approximately 5 pct of the total melted length. The effect of zone length on solute redistribution is most pronounced after a large number of zone passes. Comparison with Pfann&apos;s published data8 for solute redistribution for various Keff&apos;s and zone lengths indicates only small differences at low numbers of completed zone passes. It is evident that the expected distribution has not been realized in the case of iron. Scrapings of material deposited on the inner surfaces of the electron-focusing cage were found to be magnetic. It is, therefore, concluded that redistribution of iron is masked by evaporation. Deposition of iron inside the focusing cage was observed at all rates of zone travel. The results of the investigation may be summarized as follows: 1) Segregation of oxygen is typical for a solute with a distribution coefficient, Keff > 1. 2) No redistribution of oxygen takes place at high rates of zone travel. 3) The distribution coefficient for oxygen lies between 1.5 and 2.0. 4) Purification with respect to iron occurs mainly by evaporation. 5) The focusing cage is effective in preventing tungsten contamination.

Jan 1, 1967

By C. M. Shigley

Tan record of the largest magnesium plant in the country utilizing sea water as a primary raw material stands as another victory in the struggle for large-scale production of pure chemical elements from the oceans. Bromine was the first element to be economically and commercially recovered when, in 1933, a six million pound per year unit was built on the Atlantic Coast near Wilmington, North Carolina, by the Ethyl-Dow Chemical Co.1 The bromine was reacted with ethylene to produce ethylene dibromide, a necessary associate of tetraethyl lead in ethyl antiknock fluid. Within eight years that plant was doubled and redoubled, and another large unit was put into operation at Freeport, Texas, taking bromine from the Gulf of Mexico. In 1940, in fortunate anticipation of the impending demand for magnesium and the limitations of the production from natural brines, the Dow Chemical Co. turned again to the sea, and designed and erected a plant at Freeport to produce 18,000,000 lb. of magnesium per year from sea water.2 In March 1941, two months after the new plant had been put into successful operation, construction of an 18,000,000-lb. Government-financed addition was started. Late in 1941, as a part of the $400,000,000 defense program intended to produce 600,000,000 t0 700,000,000 lb. of magnesium per year, Dow was asked to build and operate for the Government a 72,000000-lb. plant near its original plant at Freeport. Within a few days after the Japanese made their attack at Pearl Harbor, preparation of a site was started at Velasco, Texas, for the construction of the Texas plant of the Dow Magnesium Corporation-the largest known magnesium plant utilizing sea water as its raw material. Less than six months after the first piling was driven, urgently needed magnesium was in steady production. Five months later, the plant had exceeded its rated capacity. It remained above rated production until the general magnesium curtailment was applied to Government-owned plants in September 1944. Credit for the construction and operation record of the Dow magnesium plant must be divided among the efforts of a very determined group of men, an extremely favorable location, and a simple process. It is with the two latter aspects of the plant that this article will deal. The site for the new enterprise was chosen near Velasco, Texas, on property bordering the Brazos River at a point approximately 6 miles inland from the original magnesium plant and y miles inland from the Freeport Harbor on the Gulf of Mexico. This location was far enough away from the operating units to reduce both interference from construction and the vulnerability of closely bunched manufacturing operations to the then feared air attack. Yet the distance inland was not too great for the economical construction of a barge canal from the harbor to serve both the transportation of raw

Jan 1, 1945

By J. Szekely, Robert G. Lee

Calculations are presented for the prediction of the combined radiative-convective heat loss from molten steel held in a ladle, covered by initially molten slag. A mathematical formulation is given and numerical solutions are presented of the resultant partial differential equation. It is shown that a slag layer of about 2 to 3 in. thick would prevent any significant heat loss from the top metal surface for Periods of up to 1 hr. For thinner slag layers (or in the absence of the protective slag) appreciable heat losses would occur; plots given in the paper allow the quantitative evaluation of the fall in the metal temperature due to this heat loss. The ironmaking-steel processing operation involves several intermediate steps where the molten metal is held or transfered in ladles. The quantitative assessment of the heat losses occurring under these conditions is of considerable importance in process design considerations since the temperature of the metal may have to meet rigid specifications in any given part of the processing sequence. While the metal is held in a ladle, heat is lost by two mechanisms: i) by conduction into the ladle walls; ii) by radiation and convection from the top surface. Calculations relating to the conductive heat loss, are readily made and information may be found in the literature both on data pertaining to metallurgical situations and on the techniques that are available for performing additional computations.&apos;-3 The evaluation of the combined convective-radiative heat loss is less straightforward, especially when there exists a protective slag layer covering the metal. In this latter case, as the top slag surface loses heat partial solidification may occur and the latent heat thus given up by the slag may represent an effective barrier to the heat loss from the metal. A semiquantitative assessment of the role played by the slag in preventing heat loss from the metal has been made in a previous paper,4 where it was shown that a slag layer 6 in. thick would act as a near-perfect insulator for periods of up to 2 hr. However, this first paper reported on an essentially preliminary investigation that considered only one slag layer thickness; furthermore, the boundary conditions used for the calculations were somewhat restrictive since no allowance was made for changes in the metal temperature. The purpose of this second paper is to extend the scope of the preliminary investigation previously reported by: i) considering several slag layer thicknesses; ii) allowing for variations in the metal temperature; and finally iii) by performing calculations on the net loss from the metal rather than from the slag surface. FORMULATION Consider a slag phase extending from y = 0 to y = L1, covering a metal phase that occupies the region extending from y = Ll to y = L, as illustrated in Fig. 1. Denote the slag and metal temperatures by TS and Tm and assume that initially both slag and metal are molten, having a uniform temperature Ti. At time = zero the surface represented by the y = 0 plane (top slag surface) is brought into contact with cold air, the temperature of which is given as T Thus for time > zero, heat will be transfered from the slag to the air by natural convection and thermal radiation; as a result of this heat loss the slag temperature will fall and after some time a solid phase is formed and a solidification boundary (more realistically described as a zone) will move progressively from y = 0 toward y = L1. Once the region of temperature gradients, moving ahead of the solidification zone, reach the slag-metal interface (y = L1) there will be a net transfer of heat from the metal through the slag to the cold air, across the y = 0 plane. In the formulation of moving boundary problems, involving phase changes that require computer solution, it is convenient to represent both phases by a single equation, making allowance for the latent heat of solidification by assigning an appropriate temperature dependence to the specific heat content. Thus the energy equation for the whole of the slag may be written as follows:

Jan 1, 1969

The next meeting of the Institute, the 113th meeting, will he held in Arizona in the latter part of September, 1916. All papers to be presented at this meeting must be published in the September Bulletin or previously. Manuscripts must, therefore, be in the hands of the Secretary of the Institute not later than July 1. In case manuscripts are given by authors to members of technical committees, or others, they must be in the hands of such persons sufficiently in advance so that they may be actually in the hands of the Secretary of the Institute by the date mentioned. In the past, the Secretary has received urgent requests for special consideration regarding manuscripts that come in after the closing date. In view of the obvious unfairness of this, the Committee on Papers and Publications has instructed the Secretary not to accept for presentation at the Arizona Meeting any papers received later than July 1, 1916.

Jan 4, 1916

By Grover J. Holt

A detailed description of the many variations in iron mining and transportation practice in Minnesota would require much space. Since a fairly detailed description of the practices then in use was published in the guidebook issued in connection with the meeting of the Institute on the iron ranges in 1920, and subsequent developments have been described by E. E. Hunner, M. H. Barber,2 and A. E. Anderson, J. M. Riddell and G. J. Holt,³ it will not be necessary here to do more than review the highlights of current practice. Details on any points of interest can be obtained through correspondence with the operators involved. † The iron ores of Minnesota, which have been formed through enrichment of the iron formation in which they occur, largely by the removal of silica, are usually covered by a blanket of glacial drift known locally as "surface." Surface material, including sand, clay, hardpan and boulders, makes up the greater portion of the stripping in open-pit operations. In some instances, stripping also includes taconite and paint rock," directly below the surface material and overlying the ore. Tacenite is the iron formation, a ferruginous chert with inter-bedded slate layers. :&apos;paint rock" is a local term for oxidized slate layers inter- bedded in the iron formation, high in phosphorus, alumina and moisture. The iron ores fall into two classes: (I) direct shipping (merchantable ores or ores requiring no treatment except possibly crushing or screening to make an acceptable sized product), and (2) ores requiring beneficiation (such as sintering, drying, washing, jigging, high-density treatment, or magnetic separation in the case of magnetite). The Mesabi Range produces chiefly soft Bessemer and non-Bessemer ores. The Cuyuna Range produces mainly low-manganese brown ore and high-manganese black ores, with some iron ore. The Vermilion Range yields mainly Bessemer and non-Bessemer iron ore, with some hard or lump ore that finds use in the open hearth. Open-pit mining is limited to the Mesabi and Cuyuna Ranges but underground mining is done on all three. The choice of mining methods is determined by the relative economics of overburden-removal and shaft-mining costs. Stripping Practice Common practice has been to remove the bulk of the overburden during the winter season and to mine during the summer, In- the present emergency many operators are forced to forego the economies attained by year-round utilization of paper. and to equip for, and carry on, stripping and mining simultaneously. In the normal years or lean years to come, most properties probably will be overequipped and high depreciation charges Will have to be absorbed.

Jan 1, 1943

By C. P. Mangelsdorf

The roof truss as a means of secondary or supplemental mine roof support has enjoyed increasing acceptance in recent years, particularly in bituminous coal mines. In those entries where long life is required or doubtful performance from other forms of support seems likely, trusses in many cases have provided the necessary protection for continuing operations. Although relatively expensive and time-consuming in their installation, trusses, particularly with the new resin point anchor system, appear to be justifying their higher premium. It seems inevitable that techniques and equipment for installing them within the cycle will soon be developed. The actual mechanism by which trusses contribute to the stability of a roof is, as yet, poorly understood, and it may be that more than a single mechanism is involved. There are, however, a number of useful observations which can be made concerning the structural behavior of the truss itself, based solely on the mechanics of rigid and deformable bodies. The purpose of this article is to present some of these observations, particularly relating to friction in the system. A few speculations concerning the roof must, of course, be made. From a knowledge of the structural behavior, some insight into the truss-roof interaction may be gained. The concept of the truss is quite simple. As shown in [Fig. 1], it consists of two inclined chords (usually at 45&apos;) anchored in holes drilled in the roof over the ribs. A horizontal chord is formed connecting the exposed ends of the inclined chords, either with a third piece or by bending extensions of the inclined chords until they meet in the middle. A distinction can be made between active and passive chords of a truss depending upon the manner of installation. If the inclined chords are fully grouted and the horizontal chord is merely attached to them, it may reasonably be assumed that no significant forces exist in the truss until the roof begins to work. Such would be a completely passive system. On the other hand, if the inclined chords are anchored only at their upper extremities and the horizontal chord is formed in such a way that all three chords can be pretensioned to a significant portion of their tensile strengths then the truss may be regarded as fully active. Combinations of active and passive chords are also possible. * The discussion here is confined to the fully active truss such as the Birmingham steel rod system or the Galis wire rope truss. In both cases, pretensioning is accomplished by tightening of the horizontal chord, some of which tension is transferred to the in-

Jan 1, 1981

By Raymond Mancha

The purpose of an accurate underground pressure survey is to obtain a pressure gradient along the circuit or circuits under investigation. The pressure gradient shows the rate of pressure drop between various observation points along a circuit. This determines excessive resistance regions and the economic feasibility of correcting such conditions by cleaning airways, driving additional airways, or modifying existing airways. A pressure gradient is useful for predicting the effect on other parts of the circuit when adjusting the air regulation on any one split or when planning a field airshaft or slope or a new drift to the outcrop. A single-compartment airshaft often produces disappointing results because it relievcs only a part of the circuit instead of the over-all mine pressure. It is valuable to know how the circuit pressure drop is distributed. The underground pressure survey is used also to determine the friction coefficient for various types of airway. High precision work is required to establish these vital data for predicting the characteristics of mine pressure volume when projecting new mine developments. Methods Regardless of the type of instrument used to conduct a circuit pressure survey, the work should preferably be performed at a time when the mine is idle, in order to avoid air-flow disturbances from moving trips and cages or from the opening or closing of trap doors. Preferably the survey should be made when the barometer is comparatively steady, to restrict variation in the air specific weight at observation stations while the circuit is traversed. The two most commonly used instruments for underground pressure surveys are: (I) the altimeter; (2) the inclined manometer with hose extensions. The altimeter is sufficiently accurate for determining the underground pressure gradient and is preferable to the nianometer for such work because of greater flexibility and shorter time required for the traverse. With the altimeter it is possible to select more widely separated observation stations than is practical with the manometer, with its restricted hose extension lengths. The altimeter also permits easier travel along haulage roads between airway observation stations, avoiding badly obstructed airways. The inclined manometer is more reliable than the altimeter for establishing friction coefficients in mine airways. Manometer readings are unaffected by differences in elevations between stations, which require corrections to altimeter data. The manometer provides direct reading without temperature correction, which may or may not be true with the altimeter, depending upon the make of instrument used. The elimination of correction factors combined with the instantaneous, simultaneous and

Jan 1, 1947

By Raymond Mancha

The purpose of an accurate underground pressure survey is to obtain a pressure gradient along the circuit or circuits under investigation. The pressure gradient shows the rate of pressure drop between various observation points along a circuit. This determines excessive resistance regions and the economic feasibility of correcting such conditions by cleaning airways, driving additional airways, or modifying existing airways. A pressure gradient is useful for predicting the effect on other parts of the circuit when adjusting the air regulation on any one split or when planning a field airshaft or slope or a new drift to the outcrop. A single-compartment airshaft often produces disappointing results because it relievcs only a part of the circuit instead of the over-all mine pressure. It is valuable to know how the circuit pressure drop is distributed. The underground pressure survey is used also to determine the friction coefficient for various types of airway. High precision work is required to establish these vital data for predicting the characteristics of mine pressure volume when projecting new mine developments. Methods Regardless of the type of instrument used to conduct a circuit pressure survey, the work should preferably be performed at a time when the mine is idle, in order to avoid air-flow disturbances from moving trips and cages or from the opening or closing of trap doors. Preferably the survey should be made when the barometer is comparatively steady, to restrict variation in the air specific weight at observation stations while the circuit is traversed. The two most commonly used instruments for underground pressure surveys are: (I) the altimeter; (2) the inclined manometer with hose extensions. The altimeter is sufficiently accurate for determining the underground pressure gradient and is preferable to the nianometer for such work because of greater flexibility and shorter time required for the traverse. With the altimeter it is possible to select more widely separated observation stations than is practical with the manometer, with its restricted hose extension lengths. The altimeter also permits easier travel along haulage roads between airway observation stations, avoiding badly obstructed airways. The inclined manometer is more reliable than the altimeter for establishing friction coefficients in mine airways. Manometer readings are unaffected by differences in elevations between stations, which require corrections to altimeter data. The manometer provides direct reading without temperature correction, which may or may not be true with the altimeter, depending upon the make of instrument used. The elimination of correction factors combined with the instantaneous, simultaneous and

Jan 1, 1947

By Grover J. Holt

A detailed description of the many variations in iron mining and transportation practice in Minnesota would require much space. Since a fairly detailed description of the practices then in use was published in the guidebook issued in connection with the meeting of the Institute on the iron ranges in 1920, and subsequent developments have been described by E. E. Hunner, M. H. Barber,2 and A. E. Anderson, J. M. Riddell and G. J. Holt,³ it will not be necessary here to do more than review the highlights of current practice. Details on any points of interest can be obtained through correspondence with the operators involved. † The iron ores of Minnesota, which have been formed through enrichment of the iron formation in which they occur, largely by the removal of silica, are usually covered by a blanket of glacial drift known locally as "surface." Surface material, including sand, clay, hardpan and boulders, makes up the greater portion of the stripping in open-pit operations. In some instances, stripping also includes taconite and paint rock," directly below the surface material and overlying the ore. Tacenite is the iron formation, a ferruginous chert with inter-bedded slate layers. :&apos;paint rock" is a local term for oxidized slate layers inter- bedded in the iron formation, high in phosphorus, alumina and moisture. The iron ores fall into two classes: (I) direct shipping (merchantable ores or ores requiring no treatment except possibly crushing or screening to make an acceptable sized product), and (2) ores requiring beneficiation (such as sintering, drying, washing, jigging, high-density treatment, or magnetic separation in the case of magnetite). The Mesabi Range produces chiefly soft Bessemer and non-Bessemer ores. The Cuyuna Range produces mainly low-manganese brown ore and high-manganese black ores, with some iron ore. The Vermilion Range yields mainly Bessemer and non-Bessemer iron ore, with some hard or lump ore that finds use in the open hearth. Open-pit mining is limited to the Mesabi and Cuyuna Ranges but underground mining is done on all three. The choice of mining methods is determined by the relative economics of overburden-removal and shaft-mining costs. Stripping Practice Common practice has been to remove the bulk of the overburden during the winter season and to mine during the summer, In- the present emergency many operators are forced to forego the economies attained by year-round utilization of paper. and to equip for, and carry on, stripping and mining simultaneously. In the normal years or lean years to come, most properties probably will be overequipped and high depreciation charges Will have to be absorbed.

Jan 1, 1943

By Allan E. Martin, Harold M. Feder, Irving Johnson

The cadmium-uranium system was studied by thermal, metallographic, X-7-ay and sampling techniques; special emphasis was placed on the establishment of the liquidus lines, The single inter metallic phase, identified as the compound UCd11 melts peritectically at 473°C to form a-umnium and melt containing 2.5 wt pct uranium. The cadmium-rich eutectic (0.07 wt pct uranium) freezes at 320.6°C. Solid solubilities in uraizium and cadmium appear to be negligible. Between 473°C and 600°C the liquidus line is retograde. NO publication relating to the cadmium-uranium phase diagram was found in the literature. The establishment of this diagram was of considerable interest to us because of a possible application of the system to the pyrometallurgical reprocessing of nuclear fuels. Analysis of liquid samples, metallographic examination, thermal analysis, and X-ray diffraction analysis were used to establish the phase diagram from about 300° to 670°C. Particular emphasis was placed on the establishment of the liquidus lines. The same system was concurrently studied in this laboratory by the galvanic cell method.&apos; Both studies benefited from a continual interchange of information. MATERIALS AND EXPERIMENTAL PROCEDURES Stick cadmium (99.95 pct Cd, American Smelting and Refining Co.) contained 140 ppm lead as the major impurity. Reactor grade uranium (99.9 pct U, National Lead Co.) was most often used in the form of 20-meshspheres. This form was particularly suitable because it does not oxidize as readily as finer powder. The liquidus lines were determined by chemical analysis of filtered samples of the saturated melts. The liquid sampling technique is described elsewhere2 alumina crucibles (Morganite Triangle RR), tantalum stirring rods, tantalum thermocouple protecthecadmiumtion tubes, Vycor or Pyrex sampling tubes, and grades 60 or 80 porous graphite filters were used. Uranium dissolves in liquid cadmium rather slowly. In order to achieve saturation of the melts it was necessary to modify the procedure of Ref. 2 by the use of more vigorous stirring and longer holding periods (at least 3 hr) at each sampling temperature. The samples were analyzed for uranium by spectro-photometry (dibenzoyl methane method) or by polar- ography. The analyses are estimated to be accurate to 2 pct. Thermal analysis was performed on alloys contained in Morganite alumina crucibles in helium atmospheres. Standard techniques were employed; heating and cooling rates were about 1°C per min. For the determination of the peritectic temperature, Cd-10 pct U charges were first held for at least 50 hr at temperatures in the range 435° to 460°C to form substantial amounts of the intermediate phase. For the determination of the effect of cadmium on the a-p transformation temperature of uranium, charges of Cd-25 pct U (-140+100 mesh uranium spheres) were first held near the transformation temperature, with stirring, to promote solution of cadmium in the solid uranium. The holding times and temperatures for these treatments were 18 hr at 680°C for the cooling run and 28 hr at 630°C for the heating run. Alloy specimens for X-ray diffraction and metallographic examination of the intermediate phase were prepared in sealed, helium-filled Vycor or Pyrex tubes. Ingots from solubility runs and thermal analysis experiments also were examined metallographically. Crystals of the intermediate phase were recovered from certain cadmium-rich alloys by selective dissolution of the matrix in 20 pct ammonium nitrate solution at room temperature. Temperatures were measured with calibrated Pt/Pt-10 pct Rh thermocouples to an estimated accuracy of 0.3°C. However, the depression of the freezing point of cadmium at the eutectic is estimated to be accurate to 0.05°C because a special calibration of the thermocouple was made in place in the equipment with pure cadmium just prior to the measurement. EXPERIMENTAL RESULTS The results of this study were used to construct the cadmium-uranium phase diagram shown in Fig. 1. This diagram is relatively simple; it is characterized by a single intermediate phase, 6 (UCd11), which decomposes peritectically, and which forms a eutectic system with cadmium. The solid solubilities in the terminal phases appear to be negligible. An unusual feature of the diagram is the retrograde slope of the liquidus line above the peritectic temperature. The Liquidus Lines. The liquidus lines above and below the peritectic temperature are based on three separate solubility experiments. The data are shown in Fig. 1 and are given in Table I. It is apparent from the figure that the solubility data obtained by the approach to saturation from higher temperatures fall on substantially the same lines as those obtained

Jan 1, 1962

By W. G. Pfann

Formation and slow solidification of a molten zone in a homogeneous ingot produces a discontinuity in solute concentration at the boundary of the zone and a gradient of concentration within the zone. By using two solutes, one a donor, the other an acceptor, step or graded pn barriers can be produced. EXPLOITATION of the difference in concentration between a molten solution and the solid which freezes from it is continued in this paper. The normal segregation which results from this difference has been used for purification&apos;.&apos;2 and for pn barrier-formation in semiconductors."4 By means of traveling molten zones this difference has been used to effect multistage separations and to eliminate segregation in ingots." a It will be shown here that by means of stationary molten zones this difference can be used to produce discontinuities in concentration. In particular it will be shown that a pn or npn barrier can be made by the simple act of melting and refreezing a portion of a block of semiconductor, provided that the block contains proper concentrations of a donor and an acceptor in solid solution. Assumptions The operation of melting and slow refreezing will be called remelting and the interface between liquid and solid at the start of refreezing will be called the remelt bormdary. While remelting may be done for various shapes of starting crystal and remelt zone it will be assumed that the remelt zone is cylindrical, its length being measured in the direction of freezing, which is normal to the remelt boundary, and

Jan 1, 1955