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By Howard Martens, Pol Duwez

IN two papers published in 1949, alloys of chromium with the refractory metals tungsten, molybdenum, tantalum, and columbium were investigated in view of their possible use as high temperature resisting materials. For the Cr-Ta system, a partial phase diagram was presented and the only intermediate phase was identified at Ta2Cr3. A phase of the same composition was also observed in the Cb-Cr system. The X-ray diffraction data presented in these papers, however, were insufficient for crystal structure determination. It is shown in the present study that the only intermediate phase in both the Ta-Cr and the Cb-Cr systems corresponds to the ideal stoichiometric ratio TaCr2, or CbCr2. Both structures are cubic, MgCu, type. At high temperature, however, TaCr2 has a hexagonal MgZn, type structure, which can be retained at room temperature by fast cooling. The alloys were prepared by melting in a helium arc furnace on a water-cooled plate. The design of the furnace was essentially the same as that described in ref. 3. Some alloys were also obtained by sintering compacts made of the mixed powders pressed at 80,000 psi. The sintering was carried on for 4 hr at 1375°C. The tantalum and columbium powders were supplied by Fansteel Metallurgical Corp., North Chicago, 111. The tantalum powder was the reagent grade, with a particle size smaller than 400 mesh and a total impurity content less than 0.1 pct. The columbium powder was smaller than 325 mesh and contained approximately 0.1 pct C and traces of Fe, Ti, and Zr. The electrolytic chromium powder from Charles Hardy, Inc., New York, was smaller than 300 mesh and contained about 0.1 pct Na, 0.05 pct Ca, and traces of Cu, Al, Mg, Si, and Co. Powder diffraction patterns were obtained with a 14.32 cm camera, using copper Ka radiation filtered through nickel foil. The powder pattern of the TaCr2 alloy obtained by sintering at 1375'C was different from that obtained on the same alloy rapidly cooled from the melt. Contrary to this result, the powder pattern of CbCr2 was the same, whether the alloy was made by sintering at 1375°C or by melting, and was similar to that of the TaCr, sintered. It was also found that the structure of the TaCr2 specimen obtained by melting was retained after heating for 4 hr at 1590°C, but transformed into the structure found in the sintered specimen after heating for 4 hr at 1375°C. Hence, the structural change of TaCr2, appears to be a reversible polymorphic transformation. CbCr2 and ToCr2 Structure, Low Temperature Form By using large scale Hull-Davey charts, the powder pattern of CbCr, and of the low temperature form of TaCr2 were readily interpreted on the basis of a face-centered cubic lattice with a parameter of approximately 6.95 kX. The indices of the reflections together with the values of sin' 0 are given in Tables I and 11. From this list of observed reflections, it appears that the (200), (600), (024), (046), and (028) reflections are missing. The lack of (h00) reflections for h 4n indicates a four-fold screw axis. The missing (Okl) spectra for k + 1 An indicate the existence of a diamond glide d. The combination of these symmetry elements can be found in the O— Fd3m space group, which is therefore the most probable one. After having determined the approximate density of TaCr, by the immersion method, the number of molecules per unit cell was calculated and found to be nearly eight. This information, added to the fact that the most probable space group is O leads to the consideration of a structure of the MgCu2 type, in which the atoms have the following positions: 8 magnesium in a and 16 copper in d. On the basis of this structure, intensities were computed by means of the usual formula: 1 cos'20 I a sin2 cos where F is the structure factor; 8, the Bragg angle: and p, the multiplicity factor. As shown in Tables I

Jan 1, 1953

By P. R. Celmer, Leonard R. Weisberg

THE principle of fractional crystallization has been successfully used to prepare high-purity (99.999 pct) Ga. Hoffman and Scribnerl removed single crystals of gallium solidifying in a gallium melt, while Zimmerman2 grew single crystals from the melt by the Kyropolous technique. In contrast, attempts at purifying gallium by zone refining have been less successful. ichards, reported that despite the passage of 40 zones through a gallium ingot, there still remained 5 to 70 ppm each of Cu, Fe, Ca, Mg, Si, Al, and Ag. Previously, Detwiler and Fox4 detected only one impurity, Pb, segregating in zone-refined ingots. These surprising results prompted an investigation of the factors controlling impurity segregation in gallium. Possible reasons for this were insufficient diffusion of impurities in the melt; recontamination of the melt by its oxide film which is not affected by the passage of the zone; reaction of gallium with the boat; sudden freezing of gallium following supercooling, especially since gallium easily supercools to and trapping of impurities at grain boundaries. Impurity segregation tests were carried out by directionally freezing gallium using the Bridgman rnethd, modified in that the molten gallium is lowered out of a furnace into a slush of dry ice and trichloroethylene, thus minimizing supercooling. Since the gallium is contained vertically, the oxide film is in contact only with the tail end of the melt. It was found that Teflon makes an excellent crucible for gallium since it is quite pure, non-reactive, translucent, flexible, machinable, and is not wet by gallium. The gallium crystals could be grown at various speeds, and the melt could be vigorously stirred by a Teflon rod moving through the gallium in a vertical reciprocating fashion. Single crystals could be grown by placing a solid Teflon plug at the bottom of the melt drilled out in such a way to cause the solidifying gallium to follow a winding path. Thus, even if many crystals are originally nucleated, only one grain will predominate. The grain structure of the gallium crystals was revealed by an etchant composed of equal volumes of HC1, HNO3 and HF, diluted with water to half strength. Emission spectrographic analyses were carried out on samples removed from the front and tail ends of the resulting gallium ingots. Typical results of this study are summarized in Table I. The rate of freezing in all three cases was about 1 in. per hr. It can be seen that even though stirring of the melt does help, it is even more important to grow a single crystal of Ga in order to obtain good segregation of impurities. The effect of crys-tallinity on the segregation of impurities was previously observed6 in the directional freezing of germanium; however, in this case, the effect was much less pronounced. This dependence of impurity segregation on the crystalline perfection of Ga may be related to its thermal conductivity which is the most anisotropic of all metals.7 The anisotropic thermal conductivity can cause the solid-liquid interface to be nonuniform, thus leading to trapping of impurities during freeing, and therefore reduced segregation. In conclusion, it is indicated that zone refining of gallium would be more successful if seeding and similar precautions are taken to insure single crystal growth. The authors are indebted to Mr. H. H. Whitaker for the spectrographic analyses and to Drs. B. Abeles and F. D. Rosi for helpful advice and encouragement throughout the course of this work. This research was supported by the Electronics Research Directorate, Air Research and Development Command, under Contract No. AF33(616)-5029. REFERENCES 'J. 1. IToffmon and B. T. Scribrer: I. Research h'atl. Bur. Standards, 1935, "01. 15, p. 205. 'W. Zirnmerman: Science, 1954, vol. 119, p. 41. %J. L. Richards: Nature, 1956, vol. 117, p. 182. 'D. P. Detwiler and W. M. Fox: I. Metals, 1955, "01. 7, p. 205. 5P. W. Bridgman, Proc. Am. ilcod. Sci., 1925, vul. 60, pp. 305,385,423. "S. L1. Christian: private c ommuni cation. 'K. W. Powell: roy. Sac., 1951, vol. 209, p. 525. 'W. G. Pfann: Zone Re fining, p. 20. John Wiley and Sons, Inc., New York, L058.

Jan 1, 1962

By Howard N. Eavenson

ALL of the matters so far taken up by the Institute Committee on Stabilization of the Coal Industry will be of help, but it seems to be that under present conditions not very much can be expected until the railroad situation has been improved. As an instance of this, I would cite the fact of our experience at our mines in West Virginia and Kentucky. During 1917 and 1918 at our West Virginia plants we produced for our own consumption, practically entirely in the Chicago district, about 4,750,000 net tons of coal. In 1919 our output was reduced to 3,500,000 tons, this being caused partly by the shortage of orders in the few months following the armistice, but more particularly by The car shortage which began last September and continued throughout the remainder of the year, with the exception of December. This car shortage has been more acute since the first of the year, and while we now have an actual capacity here of 20,000 tons daily and have the equipment to produce it, with the possible exception of a few houses, we are able to average only about 12,000 tons, and in consequence, about 30 per cent. of our by-product ovens in the Chicago district are idle, and a number of blast furnaces are down for the want of coke. These figures, of course, refer to conditions before the strike of switchmen in April was started.

Jan 1, 1920

By Vincent P. Gianella

THE most intense earthquake on the Pacific coast in the last several years, and probably the second most intense shock to occur in Nevada since it was settled, was felt in many Western States shortly after 10 p.m. on Dec. 20, 1932. Be- cause the rifted area contered about the northern end of Cedar Mountain it is referred to as the Cedar Mountain, Nevada, earthquake. An idea of the intensity of the shock may be gathered from the distance at which it was felt: in Wyoming, Utah, Idaho, Nevada, Washing- ton, Oregon, California and Arizona. It is the strongest quake centering in Nevada since the Pleasant Valley earthquake on Oct. 2, 1915. Despite the strength of the vibrations and the large area over which they were felt, relatively little damage was done. The extent of the damage consisted of a few old stone buildings demolished as shown in Fig. 1, much cracked and fallen plaster, many chimneys shaken down and considerable cracking of brick walls. There were no deaths and four people were but slightly injured. The small amount of damage was due, largely, to the scarcity of structures within the area of strong vibrations, but an important factor was the aridity of the region (see Fig. 2) and the shallowness of soil cover so that there was but little water-saturated loose material in which strong secondary vibrations could be formed. Had this earthquake occurred in a region of heavy precipitation and dense population the damage to property and loss of life would undoubtedly have been large, with consequently much more newspaper publicity.

Jan 1, 1933

By Paul M. Tyler, Herbert R. Mosley

Strategically situated in almost the heart of the leading fertilizer-consuming area of the United States, Tennessee long has ranked second only to Florida as a phosphate-producing state. Since 1932 its share of the national output of phosphate rock has increased steadily, and in 1937 its production mounted to an all-time record. More significant even than the increase in tonnage are the forward strides in technology. The Tennessee Valley Authority's research program has led to quasicommer-cia1 operations using hydroelectric power to manufacture concentrated phosphatic fertilizer that is used to further the farmer education program designed to streamline the fertilizer business and halt the appalling waste of farm land by soil erosion. Even more stimulating to chemically minded imaginations is the production of elemental phosphorus by a private company that not only has succeeded in extracting it from the phosphate rock in electric furnaces but actually has contrived to capture it and to transport it safely in tank cars. New values have been created for low-grade phosphate deposits, and the economic life of reserves has been lengthened while the waste of former years goes back into the mills for recovery of its values by modernized methods. Tennessee's phosphate-mining industry dates from the discovery of blue rock in Lewis County in December 1893. Its known reserves are of the order of 101,500,000 tons, which compares with the production of 825,099 tons in 1937; that is, 21 per cent of the phosphate-rock output of the whole nation. The total output reported from 1894 until July 1. 1938, was approximately 19,000,000 tons. Offcial estimates of reserves are overly conservative and evidence submitted before a joint Congressional committee in November 1938 places "probable" reserves at more than 6,000,000,000 tons.

Jan 1, 1942

By D. J. Carney, E. C. Rudolphy

IT has been demonstrated that inclusion size, distribution, and composition affect the machin-ability of resulphurized steels. Merchant and Zlatinl concluded that large sulphide inclusions aided machining by forming a (lubricating) coating on the tool face. Boulger et al.² and Van Vlack³ noted that the size, distribution, and composition of the inclusions in the steel affected the machinability. Steel specimens containing large globular sulphide inclusions usually exhibited excellent cutting properties, while machinability was adversely affected by the presence of numbers of oxide-type inclusions. Consequently a thorough knowledge of all the factors which affect the inclusions in the final product is desirable. Since almost all the inclusions have their origin in liquid steel, it was necessary to begin a study of inclusions in free-machining steels by studying the inclusions and chemical segregation in the as-cast ingot. Very little information is available on the size, distribution, shape, and composition of inclusions in large, capped, free-machining steel ingots, particularly the B1113 grade. Gregory and Whiteley4 made a general study of the inclusions in a small, high sulphur, free-machining steel ingot. Also, numerous authors have described the solidification and segregation characteristics of the four basic types of steel ingots, namely, rimmed, capped,7 semikilled,7,8 and killed7,9,10 ingots. Most of these studies were made with plain carbon or low alloy, low sulphur steel. It was desirable to study not only the ingot but also the change in size, shape, and number of inclusions on rolling an ingot to a bloom and thence to a billet. This procedure was followed and it is hoped that this study may serve the dual purpose of adding to the general knowledge of ingot solidification as well as contributing to the knowledge of the size, shape, distribution, and composition of inclusions from the ingot to the billet in a high sulphur, free-machining steel. Procedure A 12.000-lb 23x35x75 in. slab ingot of the B1113 grade was cast, sectioned, and studied both macro-scopically and microscopically. An adjacent ingot from the same heat and of the same size was rolled to a 77/8x77/8 in. bloom and thence to a 21/2x21/2 in. billet. These various bloom and billet sections were also sectioned and studied macroscopically and microscopically. Sectioning the Ingot: The ingot herein described was obtained from the United States Steel Corp.'s South Works Bessemer Blow No. 0193, a B1113 mechanically capped heat. The 23x35 in. ingot (No. 2) was teemed according to normal procedures and after stripping and transportation to the rolling mill was not placed in the soaking pit but allowed to air cool in an upright position. When completely solidified, the ingot was cut into sections by means of a powder scarfing torch and further sectioned by saw cutting as indicated in Fig. 1. Cut No. 2 (1x10x12 in.) from sections A through H was cleaned thoroughly, macroetched in a solution of 50-50 water and hot muriatic acid and used to obtain a macrograph of a horizontal section from the surface to slightly beyond the center of the 23-in. ingot dimension. Cuts No. 5 and 3 (lx81/2xl0 in. each) from sections A through H were treated in a similar manner to obtain a macrograph of a horizontal section from the surface to slightly beyond the center of the 35-in. ingot dimension. The composite macrograph of these horizontal ingot sections, which shows a vertical section of the ingot from top to bottom, is shown in Fig. 2. It should be noted that sections No. 2 are normal to sections 5 and 3 in the composite. Drillings for chemical analyses were obtained from selected positions within the above-mentioned ingot sections as noted in Fig. 3. The oxygen content was determined by the vacuum-fusion method. Samples for microscopic examination were cut from

Jan 1, 1954

By Herbert R. Mosley, Paul M. Tyler

Strategically situated in almost the heart of the leading fertilizer-consuming area of the United States, Tennessee long has ranked second only to Florida as a phosphate-producing state. Since 1932 its share of the national output of phosphate rock has increased steadily, and in 1937 its production mounted to an all-time record. More significant even than the increase in tonnage are the forward strides in technology. The Tennessee Valley Authority's research program has led to quasicommer-cia1 operations using hydroelectric power to manufacture concentrated phosphatic fertilizer that is used to further the farmer education program designed to streamline the fertilizer business and halt the appalling waste of farm land by soil erosion. Even more stimulating to chemically minded imaginations is the production of elemental phosphorus by a private company that not only has succeeded in extracting it from the phosphate rock in electric furnaces but actually has contrived to capture it and to transport it safely in tank cars. New values have been created for low-grade phosphate deposits, and the economic life of reserves has been lengthened while the waste of former years goes back into the mills for recovery of its values by modernized methods. Tennessee's phosphate-mining industry dates from the discovery of blue rock in Lewis County in December 1893. Its known reserves are of the order of 101,500,000 tons, which compares with the production of 825,099 tons in 1937; that is, 21 per cent of the phosphate-rock output of the whole nation. The total output reported from 1894 until July 1. 1938, was approximately 19,000,000 tons. Offcial estimates of reserves are overly conservative and evidence submitted before a joint Congressional committee in November 1938 places "probable" reserves at more than 6,000,000,000 tons.

Jan 1, 1942

By P. M. Robinson, M. B. Bever

THE heats of formation at 273°K of the compounds InBi, In2Bi, and TIBi2 have been determined by metal solution calorimetry with bismuth as solvent. The published information on the thermody-namic properties of these compounds is limited. The structure of the compound InBi (mp, 383°K) is tetragonal of the PbO (B10) type.1 The compounds In2Bi (mp, 362°K) and TIBi2 (mp of highest-melting composition, 486°K) are now believed to have structures of the NizIn (B8) type273 and not the A1B2 (C32) structures reported earlier.4, 5 The compounds In2Bi and TIBi2 have limited homogeneity ranges at room temperature, while the compound InBi has no detectable homogeneity range.' Samples of the compounds were prepared from 99.99 pet Bi (Mallinckrodt Chemical Works), 99.999 pet in (American Smelting and Refining Co.), and 99.99 pet Tl (Amend Drug and Chemical Co.) by melting the components in sealed, evacuated Vycor tubes. The compounds InBi and in2Bi were of the stoichiometric compositions. The compound TIBi2 contained 40 pet T1; this composition was chosen because at room temperature the alloy of stoichiometric composition does not lie within the homogeneity range.' The melts were held approximately 50°C above the liquidus for 8 hr and then quenched into iced brine. The samples were homogenized for 48 hr at temperatures 20°C below the temperature of complete solidification. Metallographic examination of sections taken from the center and the ends of the ingots did not reveal second phases or segregation . The heats of formation were determined as the difference in the heat effects on solution of a compound and of a mechanical mixture of its components added from the reference temperature of 273°K to liquid bismuth at 623°K. The details of the calori-metric procedure and method of calculation have been described elsewhere? The calorimeter was calibrated by adding bismuth at 273°K to the bismuth bath at 623°K. The calculated values of the heats of formation of the compounds, listed in Table I, are based on a value of 4.96 keal per g-atom for the difference between the heat contents of bismuth at 273" and 623oK7 No published values are available for the heats of formation of the compounds InBi and In2Bi. Hultgren et a1.7 have calculated a value of -0.50 i 0.10 keal per g-atom for the heat of formation at 423°K of the compound TIBi2 containing 40 at. pet T1 from heat-content measurements in the range from 398" to 700°K and the heats of formation of the liquid alloy. The difference between this value and the value of -0.66 * 0.01 keal per g-atom at 273°K is too large to be attributed to a difference between the heat capacities of the compound and the components over the temperature range 273o to 423oK7 However, the direct determination of the heat of formation by a calorimetric method should give a more accurate value. The heats of formation at 273°K of the compounds InBi and In2Bi lie on a straight line when plotted as a function of composition, Fig. 1. The compound In2Bi, therefore, appears to be barely stable with respect to its neighboring phases. In order for the free energy vs composition curve to be concave towards the composition axis, the entropy change on formation of In2Bi must be more positive than that on formation of InBi. As the compounds are ordered,2, 3, 8 there is no configurational entropy change on formation. The difference between the entropy changes on formation of the two compounds, therefore, is probably associated with the vibrational entropies. In view of the low heats of formation, the changes in vibrational entropy, due to changes in bond strength on formation of the two compounds, are likely to be small. Owing to the volume contractions on formation of the two compounds,5 the vibrational entropies probably decrease slightly but the decrease of the vibrational entropy of InBi is expected to be larger than that of In2Bi.

Jan 1, 1965

By R. H. Frazier, C. H. Lorig, F. W. Boulger

This investigation establishes the effect of ferrite grain size resulting from various heat treatments on the transition temperature of a semikilled steel plate. Different austenitizing temperatures and various cooling rates were used. The ductile-brittle transition temperatures were determined by the Navy tear test and the keyhole Charpy test. THE data presented in this paper deal with quality characteristics of ship-plate material which were investigated in a research project sponsored at Battelle by the Bureau of Ships, Dept. of the Navy. Specifically, the object of this investigation was to establish the effect of ferritic grain size (resulting from various heat treatments) on the so-called transition temperature of ship-plate steel. Transition temperature is not a fixed property of steel. It is derived from a series of static or dynamic tests made at various temperatures and is qualified by specifying the type of test employed as well as the testing criteria. Because in earlier investigations of ship-plate quality1,2 the so-called Navy tear test and standard notched-bar tests (keyhole Charpy) proved to be useful in interpreting instances of brittle behavior of ship plate in service, these tests were used in the investigation reported in this paper. By definition,' in the Navy tear tests the highest temperature at which one or more of four specimens breaks with a brittle fracture (that is, when less than 50 pct of the fracture area has a dull fibrous texture) is termed "transition" temperature. In the Charpy tests, the 12 ft-lb level of energy absorption was used as a criterion indicating the "transition" temperature, although other levels of energy absorption were also used for comparison. Earlier work" on ship-plate steels indicated that the temperature at which ship plate is finished has a very significant effect on its notched-bar properties. Plates rolled in the laboratory, where the finishing temperature can be carefully controlled, showed a 16°F decrease in tear test transition temperature when the finishing temperature was lowered 200°F (from X" to Y°F). The same plates showed a drop of 10°F in the keyhole Charpy transition temperature from the same decrease in finishing temperature. Commercially finished plates' exhibit a similar trend. When the ferrite grain size of the hot-rolled laboratory plates was determined, a close relationship was found between the ferrite grain size and the notched-bar transition temperature." " he indicated relationship between grain size and transition temperature was in agreement with the findings on low carbon steels of Hodge, Manning, and Reichhold' despite the differences in composition of the steels. The cooling rate after rolling varies from one steel plant to another. This variation changes the micro-structure" and appears very likely to affect the notched-bar properties of the steel plates. In the investigation summarized in the present paper, heat treatments simulating finishing practices in the hot rolling of ship plate were used in order to vary the ferritic grain size. It is believed that the indicated relationship between grain size and transition temperatures of the ship-plate material will prove useful in estimating the effect of rolling temperature and of cooling rates from rolling temperatures on the notched-bar properties of semikilled steel plate. Material The semikilled steel plate used in this investigation was a ¾ in. hot-rolled plate from an open hearth heat. Other plates from this heat have been used on many other studies performed for the Ship Structure Committee," "," and the heat has been identified as project steel "A". The chemical composition of the plate1 was 0.25 pct C, 0.49 pct Mn, 0.011 pct P, 0.045 pct S, 0.04 pct Si, and 0.004 pct N.

Jan 1, 1956

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 Louis V. Bender

THIS paper gives a short review of the installation for and the use of gas, as a. fuel, at the Anaconda Reduction Works of the Anaconda Copper Mining Co. Before putting in gas tile fuels used were pulverized coal, lump coal, coke distillate and oil. These fuels are now almost entirely eliminated. For nearly fifty years bituminous coals from Wyoming and Montana fields had been used. These coals were of a good grade, analyzing 11,300 B.t.u. and having an ash content of 12 per cent. When hydro-electric power replaced steam-driven equipment, the coal requirements were reduced; and, on account of improvements in metallurgy and/ or in furnace design, the quantity was lessened. Later, oil and distillate were introduced and used in some of the operations. All of these things tended toward the lessening of the amount of coal used, and had it not been for the increase in the size of the plant, the tonnage used would have been small when the change was made to gas.

Jan 1, 1932

By AIME AIME

THE value to the engineering profession of a liaison between the engineering societies of Russia and America, through Engineering Council, was the subject of a meeting in the Engineering Societies Building attended by over 500 persons. In introducing the subject, Mr. N. A. Stephanoff, President of the Russian Society of America, said: In Russia, engineers were divided into two classes: those who had graduated from the high technical schools and the practical engineers who had graduated from special technical schools. These technical schools were divided into three groups: The first corresponded to the German polytechnical schools with many departments, mechanical, chemical, metallurgical, mining, etc. The second group corresponded to the French special schools of the "Écoles des Ponts et Chaussées." "École des Mines." The third group was formed by the Military and Naval Academies of Engineers. In 1910, Russia's high technical schools had about 45,000 students, whose training covered a period of not less than five years, and who enjoyed all opportunities afforded by laboratories in no way inferior to those of Germany.

Jan 1, 1920

By D. G. Russell

A simple method has been developed with which flowing bottom-hole pressure data from two-rate flow tests in oil or gas wells can be analyzed to estimate the formation permeability, skin factor and average reservoir pressure. The required pressure data are obtained by observation of the transient bottom-hole pressure behavior after the stabilized producing rate of the well is changed to another, higher or lower, rate. The new method yields the same information as a conventional pressure buildup analysis, but eliminates the need for closing in the well. The analysis of a two-rate flow test is of the same degree of difficulty and requires about the same engineering time for application as a conventional pressure buildup analysrs. The extended closed-in periods experienced with conventional buildups because of long, low-rate afterproduc-tion periods are eliminated by fIow tests. Other anomalous pressure buildup effects, such as "humping" due to weli-bore phase segregation, can be successfully eliminated with the new method. Generally, flow tests of about 24 hours' duration run with conventional pressure measurement equipment are sufficient for interpretation purposes. Field testing of the two-rate flow test method has established that it is a reliable and economical method which can be used in many instances to complement or even replace conventional pressure buildup methods. INTRODUCTION The principal method for estimating formation permeability and well damage, or skin factor, in a producing oil or gas well is the analysis of shut-in bottom-hole pressure buildup data.' This familiar method has been used quite successfully by reservoir engineers for many years. It is based on the solution of the radial flow equation for constant rate conditions, and requires that the well be closed in for a sufficient period of time to obtain a clearly defined linear portion on the plot of observed t + ?t bottomhole pressure vs log t + ?/?t(where At is shut-in A? time, and t is producing time to the instant of shut-in). From the slope of the plot and other normally obtainable data, the permeability, skin factor, and reservoir pressure at infinite shut-in time (if the reservoir were infinite) can be estimated. Over the years several drawbacks have become apparent in the use of conventional shut-in pressure buildups for determining permeability and skin factor. The conventional pressure buildup interpretation theory assumes that a well is closed in at the sand face and that no production into the well occurs after shut-in. In practice, of course, the well is closed in at the surface, and inflow into the well continues until the well fills sufficiently to transmit the effect of closing in to the formation. This adjustment period is commonly referred to as the "after-production" portion of the pressure buildup. In the tight reservoirs, long, low-rate after-production periods frequently occur, and the well must be shut in for several days or, in some instances, even weeks to obtain an interpretable buildup curve.' Obviously, such long shut-in times can cause loss in current income, both from reduced oil production and from the fact that personnel and pressure measurement equipment are occupied with a single well for too long a time. In other cases, even long shut-in periods do not seem to be of much aid in obtaining an interpretable buildup." If there is considerable phase redistribution (liquid fallout or bubble rise) after a well is shut in, then curves with no interpretable portion are often obtained during the buildup. In addition to instances in which wellbore effects cause trouble, there are also cases in which the major objection to use of the closed-in pressure buildup is simply the fact that the well must be shut in. When there is no proration and when the well has limited producing capacity. closing in the well means loss of income. From the foregoing discussion it is apparent that it ib desirable to have an alternative method of obtaining the same information as that derived from a conventional buildup without the need of closing in the well. One possible solution which has been offered for this problem is the use of a bottom-hole shut-in tool' which isolates the major portion of the flow string from the formation face during the buildup. In this paper an alternative method which is frequently successful in avoiding wellbore effects and which does not require the use of special equipment is presented. A new, simple method has been developed with which the flowing bottom-hole pressure data from flow tests in oil or gas wells can be used to estimate permeability, skin factor and the average reservoir pressure. The required pressure data are obtained by observation of the transient bottom-hole pressure behavior after the stabilized production rate of the well is changed to another, higher or lower rate. The need for closing in the well is eliminated, and pressure measurement periods of only 18 to 24 hours arc usually sufficient, even in tight reservoirs. Thus, the new

By H. T. Shore, J. M. Schultz

A number of experimental rnethods—X-ray powder diffractometry, Laue photography, X-ray small-angle scattering, and transmission electron microscopy and dijfraction—have been utilized to examine the morphology associated with precipitation from the terminal, g, solid solution of a Zn-1 pct Cu alloy. A significant age hardening was observed in a 1 pct Cu alloy. X-ray and electron diffraction results showed that the structural inhomogeneities associated with the hardening were isotructural with the matrix. The average size and shape of the inhomogeneities were deduced from the electron microscopy and X-ray small-angle scattering. The preprecipitates are hexagonal platelets some 300? in diam. and some twelve unit cells thick. The orientation of the platelets was deduced from Laue photographs and electron diffraction. The platelet plane is (0001). When a large amount of pre-precipitation is present in a localized volume the new lattice is often disoriented by a rotation about (0001) of of the matrix. WhILE dilute Zn-Cu alloys have been commercially important for some 50 years, relatively very little is known metallographically about this material. The "Zilloys", zinc with about 1 wt pct Cu and sometimes a small addition of magnesium, are used to produce rolled zinc which is harder and stronger than that produced by other rollable zinc alloys.' According to the phase diagrams of the zinc-rich side of the Cu-Zn system, such dilute Zn-Cu alloys should age-harden;2-5 the solubility of copper in zinc, g-phase, at 424°C is 2.68 pct, while at 0°C it is only to 0.3 pct. However, the published literature on the aging of this system appears to be limited to a documentation of the contraction of 1, 2, and 3 pct Cu alloys aging at 95°c,6 and an attempt to measure changes in lattice parameters during aging.' In the latter work, no lattice parameter changes were detected, although a broadening of the highest-angle lines was detected and considerable diffuse scattering was observed. Micro-structural investigations have been limited to the latest stage of aging, wherein Widmanstatten precipitates are formed.3,47 These alloys are of interest for still another reason. The two most zinc-rich phases in the Cu-Zn system, 77 and E, are both hcp. Moreover, the change in a, between 17 and t for a 1 wt pct Cu alloy is onlv 3.64 -,~ct: the change in Co is 12.0 ict. It would be anticipated that precipitation in such a material might occur through metastable phases or G.P. zones with epitaxy along mutual 0001 planes. The goals of the present work are aimed at partially filling the void of knowledge concerning the early stages of precipitation from the g phase. In particular, we have attempted to document the magnitude of the age hardening of this system and to determine the size, shape, and orientation within the matrix of the elements of precipitation in an early stage of condensation. EXPERIMENTAL A) Specimen Preparation. Specimens were prepared In two somewhat different ways, one method being used for X-ray Laue and diffractometer measurements, optical microscopy, and Rockwell hardness measurements and the other used for electron microscopy and X-ray small-angle scattering. In the first case zinc and copper in the proper proportions to yield a 1 wt pct Cu alloy were melted together in a closed graphite crucible. Castings so made were free of apparent segregation or oxidation. The castings were then solution-annealed at 400°C for several days and then quenched in water to room temperature. Filings of portions of the specimens were made for use as X-ray powder diffractometry specimens. The electron microscope material was made as follows. Castings were made under vacuum with copper powder placed inside a hollow zinc cylinder to insure good contact of the materials. These 1 wt pct Cu pieces were then rolled to 0.1 mm with an intermediate anneal in vacuo. The rolled sheets so formed were then annealed for about 6 hr at 225°C. Finally the specimens were electropolished slowly until thin enough for transmission electron microscopy. The polishing is discussed in greater detail in the Results section. B) Measurements. X-ray measurements of three types were performed. A G.E. XRD-5 diffractometer was used to examine powders of the alloy for identification of second-phase material. A Kratky small-angle camera, also operating from a G.E. tube, was used to investigate the sizes of small precipitate particles. In both cases, nickel-filtered copper radiation was utilized. Finally, individual grains of the large-grained castings were examined in the back-reflection Laue geometry. Electron microscope studies were carried out with a J.E.O.L. Model 6A instrument. RESULTS A) Hardness Measurements. Hardness measurements performed at room temperature on the large-grained polycrystalline specimens showed a hardening which was essentially complete in 3 hr. Fig. 1 shows a typical plot of hardness vs aging time. The relative magnitude of the ultimate hardening varied from run to run between 150 and 200 pct of the value for the material immediately after quenching from the solution anneal. Most probably the variations reflect small changes in the time taken to remove the specimen from the vacuum furnace after the solution anneal.

Jan 1, 1969

By Gray L. L., Max Littlefield, Godbold A. C.

The West Edmond pool of Central Oklahoma, a limestone reservoir, has an area in excess of 29,000 acres and as of Sept. 15, 1946, had produced 53 million barrels of oil from 731 wells at an average depth of 6900 ft. Water has encroached into the reservoir along the west side of the pool and although the area of water invasion is large the net volume of water influx is small, because encroachment has been primarily into a fracture system. The most significant part of this study concerns the character of the Hunton reservoir. Geological study of cores of the producing section was made to supplement core-analysis data. It was determined that approximately 90 pct of the pore volume was contained in intergranular or sand-like porosity and 10 pct in fractures (intermediate porosity). The porous limestone is divided into blocks by the fractures, although in the strongly dolomitic parts of the producing section, fractures are less well developed. The low-permeability intergranular porosity, largely subsidiary to the high-permeability fractures, will produce oil into the fractures by evolution of solution gas. The fractures in effect serve as drainage channels for production of oil from the inter-granular porosity. Because of such a large difference in permeabilities of the two com-ponents, a high degree of by-passing will occur, and, accordingly, the economics involved in undertaking full-scale high pressure gas injection operations have been seriously questioned. Introduction The West Edmond Hunton pool, which covers portions of Canadian, Logan, Oklahoma, and Kingfisher Counties in Central Oklahoma, is the largest reservoir producing oil from a limestone in the state. The total area of the pool comprises about 29,240 acres and development is considered to be essentially complete. In all, 731 producing wells have been completed in the Hunton reservoir at an average depth of approximately 6900 ft, and have yielded a cumulative oil production in excess of 53 million barrels as of Sept. 15, 1946. In addition to wells completed in the Hunton limestone, 21 wells have been completed in the Bartlesville sand at a depth of approximately 6500 ft, which have produced a total of 730,000 bbl of oil. One small producer has been completed in the Cleveland sand at a depth of 5700 ft. However, a study of only the Hunton limestone reservoir will be presented in this paper. The most significant phase of this study concerns the special type of geological core examination that was made in an effort to ascertain the type and degree of porosity in the rock in accordance with lithologic types. Results of this geological study showed the west Edmond pool to be of such a complex nature as to appreciably affect the behavior normally associated with homogeneous reservoirs. Recognition of this condition in the

Jan 1, 1948

By Max Littlefield, Godbold A. C., Gray L. L.

The West Edmond pool of Central Oklahoma, a limestone reservoir, has an area in excess of 29,000 acres and as of Sept. 15, 1946, had produced 53 million barrels of oil from 731 wells at an average depth of 6900 ft. Water has encroached into the reservoir along the west side of the pool and although the area of water invasion is large the net volume of water influx is small, because encroachment has been primarily into a fracture system. The most significant part of this study concerns the character of the Hunton reservoir. Geological study of cores of the producing section was made to supplement core-analysis data. It was determined that approximately 90 pct of the pore volume was contained in intergranular or sand-like porosity and 10 pct in fractures (intermediate porosity). The porous limestone is divided into blocks by the fractures, although in the strongly dolomitic parts of the producing section, fractures are less well developed. The low-permeability intergranular porosity, largely subsidiary to the high-permeability fractures, will produce oil into the fractures by evolution of solution gas. The fractures in effect serve as drainage channels for production of oil from the inter-granular porosity. Because of such a large difference in permeabilities of the two com-ponents, a high degree of by-passing will occur, and, accordingly, the economics involved in undertaking full-scale high pressure gas injection operations have been seriously questioned. Introduction The West Edmond Hunton pool, which covers portions of Canadian, Logan, Oklahoma, and Kingfisher Counties in Central Oklahoma, is the largest reservoir producing oil from a limestone in the state. The total area of the pool comprises about 29,240 acres and development is considered to be essentially complete. In all, 731 producing wells have been completed in the Hunton reservoir at an average depth of approximately 6900 ft, and have yielded a cumulative oil production in excess of 53 million barrels as of Sept. 15, 1946. In addition to wells completed in the Hunton limestone, 21 wells have been completed in the Bartlesville sand at a depth of approximately 6500 ft, which have produced a total of 730,000 bbl of oil. One small producer has been completed in the Cleveland sand at a depth of 5700 ft. However, a study of only the Hunton limestone reservoir will be presented in this paper. The most significant phase of this study concerns the special type of geological core examination that was made in an effort to ascertain the type and degree of porosity in the rock in accordance with lithologic types. Results of this geological study showed the west Edmond pool to be of such a complex nature as to appreciably affect the behavior normally associated with homogeneous reservoirs. Recognition of this condition in the

Jan 1, 1948

By Glenn C. Waterman

THE diamond drill is a very important tool in exploration and development testing and its use is increasing. In almost all cases results of diamond drilling are analyzed on the basis of grade and tons. A proper evaluation of core and sludge assays is important if drilling results are to be acceptable as a basis for geologic and engineering appraisal. The relatively wide variation in assay averages as calculated by various well-known combining methods indicates that the engineering choice of a method may affect the outcome of the drilling in terms of ore and waste. The problem of combining assay results from core and sludge samples has been discussed many times in conference and in the literature.'-' Most writers agree that the field of disagreement in methods is large and that the engineer on the job must consider features unique to his drilling, pick one of several combining methods, and depart from the rules when abnormal results come in. All the discussion to date can be summed up by the admission that as yet there is no fairly simple, generally acceptable combining method that is practicable over a wide range of drilling conditions, ground conditions, and ore occurrence. The combining problem is important in evaluating drilling results at Chuquicamata. Recently a reappraisal has been made of recovery variables and their effect on assays, with the result that a new combining method is offered which fits average drilling conditions and is mathematically reasonable. It is simple in application, fundamentally correct, and an improvement over most combining methods. At Chuquicamata diamond drillholes are used to outline the grade and position of blocks of normal and marginal grade oxide, mixed, and sulphide ore. Most holes penetrate all classes of material (and waste), and it is important for mining programs as well as ore reserves to know almost precisely the soluble and insoluble copper content of mineralized ground. At present three classes of ore are mined and treated differently. For an orderly sequence of mining operations which can provide regular daily tonnages of all three ore types and keep grade at certain levels with minimum variation, ore type and its grade must be predicted. Diamond drilling plus geologic mapping and bench sampling are tools for prediction. And drilling data are largely used to calculate grade of material more than a few meters away from bench faces. The orebody at Chuquicamata" is criss-crossed by millions of barren or mineralized weak to fairly strong slips and fault fissures. Mineralization is diverse and encompasses many quartz and oxide or sulphide-bearing copper veins, as well as seams and disseminated grains. Copper occurs in oxide or sulphide minerals or mixtures of these two mineral types. Rock conditions vary from intensely seri-citized (soft and porous) through clay-altered ground to almost fresh granodiorite. The result is an orebody which offers many obstacles to good and consistent core recovery in diamond drilling. Recovery varies considerably in the several alteration zones, the various types of oxide and sulphide ores, and the position and inclination of the drillhole within the complex fracture pattern. As core recovery drops sludge samples must be used with core samples to calculate grade. Many years of drilling at Chuquicamata indicate that in good grade oxide zones and in the sulphide areas core recovery is good and the ground uniformly mineralized. Moderate loss of core, therefore, does not markedly affect grade calculations based on core assays. An early core-sludge combining method used core assays at face value as indicating grade down to 50 pct core recovery, but below this recovery percentage sludge samples were used and weighted according to the standard Longyear chart. This method apparently did not introduce serious errors, but it abruptly used sludge assays with high weighting factors representing 100 pct return irrespective of actual percentage of sludge recovered. Recent drilling activities have been directed toward outlining the marginal ore areas. The non-uniform mineralization and generally poorer core recovery in such ground indicated that a more exact core-sludge combining method was required to equate wide differences between core and sludge assays and recovery. In fringe ore areas at Chuquicamata core recovery averages about 50 pct, from a minimum of 10 to 15 pct to a maximum of 100 pct. Sludge recovery is likewise variable and averages perhaps 80 pct even though holes are cemented as water return falls off. In a homogeneously mineralized area cut by many slips and faults, with hard and soft ribs, loss of core is loss of ground which has a grade similar to that of core recovered, and core assays approximate true grade. In this case sludge samples need not be used. However, it would be unusual to know beforehand that an area is uniformly mineralized, and in fact this condition is probably uncommon. Generally the distribution of valuable minerals in the ground does not exactly compare with their recoverability in core. Thus, in the usual case, loss of core decreases the

Jan 1, 1956

By George S. Rice

MANY studies on ground movement and subsidence have been carried on by members of the Institute during the past year, but only a few papers have reached maturity. Two of the mining schools of this country have continued their interest in ground movement research. At Columbia University School of Mines, Philip Bucky has continued his investigations, employing photoelastic methods and the use of his centrifugal apparatus for testing what he termed "the strength and behavior of mining structures." Helmut Landsberg, of The Pennsylvania State College, has developed a convergence recorder similar in principle to that used by the

Jan 1, 1936

By H. H. Reamer, B. H. Sage

Attempts have been made to predict the volumetric and phase behavior of naturally occurring hydrocarbon mix-turesl-6 but these methods have not been extended to the higher pressures and tem-peratures that are currently encountered in some producing formations. Furthermore, the methods of prediction at present avail-able have not been tested in a sufficient number of cases to ensure their applica-bility to all naturally occurring hydrocar-bon mixtures, even at the lower pressures and temperatures. For these reasons the behavior of a number of hydrocarbon mix-tures from a field in which the subsurface pressures are above 4500 lb. per sq. in.t and the temperatures are in the neighbor-hood of 250°F. was investigated. Method The objective of this program was to determine the volumetric behavior of ma-terial as it existed in the reservoir as a function of pressure, temperature and com-position. Strictly speaking, this cannot be accomplished in any simple fashion. How- ever, the variations in composition that are encountered within a producing reservoir may be approximated roughly by means of mixtures made up of two arbitrarily chosen constituents. Experience indicates that the liquid and gas phases from a high-pressure gas trap afford a simple source of material for this purpose. Throughout this discus-sion the samples of the gas phase and liquid phase from the production trap will be called the "trap-gas sample" and the "trap-liquid sample," respectively. The volumetric behavior of both of the trap samples was determined throughout the temperature interval between 100" and 250°F. at pressures up to 5000 lb. per sq. in. In addition, the behavior of eight different mixtures containing varying proportions of the two trap samples was studied throughout the same temperature and pressure intervals. The experimental results yielded information concerning the specific volume of the material as a function of pressure, temperature and the relative quantity of the trap samples. The relative amount of each of the paraffin hydrocarbons of lower molecular weight than n-hexane was determined for each of the trap samples. In addition, the specific weight, viscosity and average molecular weight of the hexanes-and-heavier fraction of the trap-liquid sample were determined as well as similar information for each of five fractions separated from this material by distillation. From these data the weight fractions of each of the components from methane through pentane were determined for the trap samples and eight systematically chosen mixtures. Materials The gas and liquid samples were obtained from the production trap of a well in the Rio Bravo field in California during the fall of 1939. Information concerning the condi- 70

Jan 1, 1941

By H. H. Reamer, B. H. Sage

Attempts have been made to predict the volumetric and phase behavior of naturally occurring hydrocarbon mix-turesl-6 but these methods have not been extended to the higher pressures and tem-peratures that are currently encountered in some producing formations. Furthermore, the methods of prediction at present avail-able have not been tested in a sufficient number of cases to ensure their applica-bility to all naturally occurring hydrocar-bon mixtures, even at the lower pressures and temperatures. For these reasons the behavior of a number of hydrocarbon mix-tures from a field in which the subsurface pressures are above 4500 lb. per sq. in.t and the temperatures are in the neighbor-hood of 250°F. was investigated. Method The objective of this program was to determine the volumetric behavior of ma-terial as it existed in the reservoir as a function of pressure, temperature and com-position. Strictly speaking, this cannot be accomplished in any simple fashion. How- ever, the variations in composition that are encountered within a producing reservoir may be approximated roughly by means of mixtures made up of two arbitrarily chosen constituents. Experience indicates that the liquid and gas phases from a high-pressure gas trap afford a simple source of material for this purpose. Throughout this discus-sion the samples of the gas phase and liquid phase from the production trap will be called the "trap-gas sample" and the "trap-liquid sample," respectively. The volumetric behavior of both of the trap samples was determined throughout the temperature interval between 100" and 250°F. at pressures up to 5000 lb. per sq. in. In addition, the behavior of eight different mixtures containing varying proportions of the two trap samples was studied throughout the same temperature and pressure intervals. The experimental results yielded information concerning the specific volume of the material as a function of pressure, temperature and the relative quantity of the trap samples. The relative amount of each of the paraffin hydrocarbons of lower molecular weight than n-hexane was determined for each of the trap samples. In addition, the specific weight, viscosity and average molecular weight of the hexanes-and-heavier fraction of the trap-liquid sample were determined as well as similar information for each of five fractions separated from this material by distillation. From these data the weight fractions of each of the components from methane through pentane were determined for the trap samples and eight systematically chosen mixtures. Materials The gas and liquid samples were obtained from the production trap of a well in the Rio Bravo field in California during the fall of 1939. Information concerning the condi- 70

Jan 1, 1941