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By Whitman E. Brown, Louis J. Erck

The installation in 1948 of a Hum-phrey~ spiral concentrator section at the Hill-Trumbull plant of The Cleve-land-Cliffs Iron Co. is the latest commercial method on the Mesabi Range being used for the recovery of fine iron ore. In two stages of concentration 84 spirals treat approximately 120 long tons per hour of minus ? in. ore. These spirals augment the production of the heavy-density plant which recovers the plus 36 in. iron from the plant crude ore. Structure of the ore is such that, when crushed, about 50 pct of the plant crude is minus ? in. size. After de-sliming in a 66 in. Akins classifier, grinding the classifier product in a ball mill and again desliming in a 78 in. Akins classifier about 15 pct of the crude ore remains to be treated in the spiral plant. Overall recovery of the ball mill feed in the Hill-Trumbull spiral plant during the 1948 season was about 53 pct of the weight and 66 pct of the total iron content. Of the actual feed delivered to the spirals from the 78 in. classifier 64.9 pct of the weight was recovered containing 73.7 pct of the total iron. The average analysis of the spiral concentrate is 55.05 pct Fe and 14.83 pct SiO2. An average of mill assays during the 1948 season is given in Table 1. The Hill-Trumbull plants treat both wash ore and jig-type ore. During the 1948 season spirals were used only on the fine sizes of jig-type ore. At times the deslimed minus ? in. size is of sufficient grade to warrant bypassing the spirals but in the main the fine size is delivered to the 48 first stage spirals and thence to the 36 cleaner or second stage spirals. In the past several years numerous Mesabi Range ores in the fine size cate- gory have been tested by a wide variety of beneficiating equipment. The prodigious amount of research devoted to the recovery of values in the fine ore reflects the dire need of the iron industry to squeeze the last possible unit of iron from the mined ore and to develop suitable equipment and processes to satisfactorily concentrate the leaner horizons as they are encountered in the process of mining. Large governmental and private appropriations have been allotted, new laboratories built, research and technical staffs increased, and operator-manufacturer cooperative agreements applied to hasten the solution of the problem. The University of Minnesota, at its Eighth Annual Mining Symposium in January 1947, dedicated as its objective the bringing to light of technological developments in iron ore beneficiation. Papers were given at that time relating to processes being developed. Specifically, these papers reviewed flotation, Baum jig, selective media concentrator, Hardinge concentrator, Dorrco sizer, heavy media concentration, Hydrotator, and the Humphreys spiral. The Cleveland-Cliffs Iron Co., after encouraging results from tests in a small pilot plant using one full size spiral, made the first commercial installation of Humphreys spirals on the Mesabi Range at their Hill-Trumbull mine, Taconite, Minn. This company

Jan 1, 1950

By H. C. Fiedler

Heats of high purity iron containing 3.1 pct Si and be -tween 0.0003 and 0.0295 pct N were prepared by vacuum melting ad then pouring while in a nitrogen atmosphere with the pressure between 0 and 90 psi. Strip from a heat with 0.0184 pct N underwent complete secondary recrystallization during the final anneal. Heats with less nitrogen had too few Si3N4 particles to restrain normal grain growth, and the heat with higher nitrogen had too many particles to allow complete secondary recrystallization. In the hot-rolled structure, Si3N4 precipitates only at the grain boundaries, with the consequence that annealing after hot-rolling diminishes the ability to subsequently undergo secondary recrystallization. In contrast to this behavior, ALNprecipitates uniformly in the hot-rolled structure. Under 1 atm of nitrogen, Si3N, in 3.1 pct Si-Fe dissociates between 900" and 950°C; the solubility of nitrogen increases from 0.0010 pct at 900" to 0.0030 pct at 1200°C. The solubility of nitrogen in Si-Fe has been the subject of many investigations. Corney and Turkdogan1 heated a 2.83 pct Si alloy in nitrogen and found the solubility, under 1 atrn of nitrogen, to be 0.0019 pct at 900°C. They claimed that Si3N4 did not form in the alloy above 705°C in 1 atrn of nitrogen. Fryxell et al.2 heated samples of 3.25 pct Si-Fe containing 0.0025 pct N over a range of temperatures and then analyzed for total nitrogen by vacuum fusion and for nitrogen in solution by a modified Kjeldahl technique. At 900°C, they reported the solubility of nitrogen in equilibrium with Si3N4 to be 0.0011 pct. pearce9 found the solubility of nitrogen at 900°C under 0.95 atrn of nitrogen to be 0.0017 pct in a 3.06 pct Si alloy. He reported that Si3N4 does not form above 770°C in 1 atrn of nitrogen. Although internal friction measurements have given somewhat higher values for the solubility,4-6 if the solubility of nitrogen is as low as has been reported by most investigators, and if Si3N4 is stable up to at least 945°C at 1 atrn pressure of nitrogen as reported by Seybolt,7 a small amount of nitrogen in properly processed Si-Fe should be effective in promoting secondary recrystallization. The requirement is that in the final heat treatment there be enough small, well-dispersed particles of Si3N4 to restrain normal grain growth. Fast8 has obtained secondary recrystallization by nitriding high-purity 3 pct Si-Fe after hot-rolling to a thickness of 0.118 in., followed by processing to 0.012 in., and annealing. A large amount of nitrogen, 0.076 pct. was introduced during the nitriding heat treatment, but he has since reported9 that "a few hundredths of a percent" is sufficient. Small amounts of aluminum10 or vanadium" nitride are capable of promoting secondary recrystallization. Heats containing as little as 0.010 pct A1 or 0.042 pct V and from 0.006 to 0.009 pct N underwent complete secondary recrystallization at final gage, whereas heats with lesser amounts of aluminum or vanadium did not.l2 To be reported is the behavior of nitrogen in high-purity 3.1 pct Si-Fe, and the relation of this behavior to the ability to undergo secondary recrystallization. PROCEDURE Ingots weighing 1 lb were made by vacuum melting high-purity electrolytic iron (A104, Glidden Co.) and high-purity silicon (Monsanto Co.). The latter was used in preference to ferrosilicon to insure a low aluminum content. The design of the melting furnace permitted pouring with the furnace atmosphere either below or above atmospheric pressure. Accordingly, at the completion of melting, nitrogen was admitted to the desired pressure and the heat then immediately poured. The ingots were sound, with no indication of porosity. In Table I are listed the heats investigated, the nitrogen pressure at pour, and the nitrogen and oxygen contents as determined by vacuum fusion with a platinum bath at 1850°C, a procedure which insures measurement of the total nitrogen.13 In addition, all heats contained 3.1 pct Si and not more than 0.002 pct C, 0.003 pct S or 0.005 pct Al. It was subsequently found that the quantity of nitrogen contained in the heats in Table I does not necessarily represent that obtained under equilibrium conditions. For example, the ingot poured immediately after 1 atrn of nitrogen was admitted to the chamber contained 0.0093 pct N, whereas an ingot poured 3 min after the nitrogen was admitted contained 0.021 pct N and another poured after a 6-min delay contained 0.029 pct N. While some bleeding of the hot top occurred in the latter instance, the ingot when examined in cross section appeared sound. The ingots were heated to 1325°C in hydrogen and rapidly rolled to 0.080 in. in 3 passes. The roll speed of the final pass was reduced so as to increase the quenching effect of the rolls. The hot-rolled pieces were processed both as-hot-rolled and after heating for 3 min at 900°C in hydrogen. After cold-rolling to 0.026 in., the strips were heated for 2 min at 900°C in hydrogen, then cold-rolled to the final gage of 0.012 in. The loss of nitrogen in going from the ingot to cold-rolled strip was no more than 10 pct. The final heat treatment, which was for the purpose of develop-

Jan 1, 1970

By Earl Oliver

Some two years ago the Petroleum Division of the A. I. M. E. organized a special study of unit operation. That method of handling oil pools had been urged as the remedy that would save the United States petroleum industry from the crisis that even then loomed as more than a small cloud on the horizon. Today it is only one of several remedies vigorously advocated. Proration, regulation of imports, unit operation, constructive marketing and interstate compacts all have their earnest proponents, but the advocates of each have been disposed to look with indifference on the other respective proposals, with the result that none has had united support. Meanwhile the industry has drifted rapidly toward a serious crisis, the imminence of which in itself may bring the solution. The gravity of the situation tends to force study of the merits of proposals that a short time previously were brushed aside as impractical; and to the surprise of most of us we now find merit where previously we thought none existed. Irrespective of what might have been the result had any single proposal being adopted years ago, it is now apparent that under present conditions no one of the remedies—unit operation, proration, regulation of imports or constructive marketing—standing alone would be of much benefit. On the other hand, it is becoming evident that a well balanced program comprising all four of these remedies might save the United States petroleum industry; also that some such comprehensive program might be necessary to save it. It is even becoming evident that the despised interstate compact might be an appropriate type of machinery in which to group and coordinate all these remedies. We have progressed beyond the belief that either the industry or the government working alone can correct the situation, and have arrived at the more healthy realization that the task will require most sympathetic cooperation between government and industry, backed by an equally sympathetic public understanding. If we were functioning under a Mussolini or a Stalin, stabilizing the petroleum industry would be a much simpler task. However, in the

Jan 1, 1931

By J. L. Huitt

Some of the problems associated with the acid treatment of oil wells are related to the control of the composition of formation treating acid. One test usually made at the well site is the determination of the acid concentration. Heretofore, the concentration of the acid delivered to the well site usually has been interpreted from a hydrometer measurement of the specific gravity of the acid solution. Experience has shown that this indirect measurement of acid concentration can give erroneous results. More reliable results are, of course, obtainable by the titration method; however, this method is not easily adapted to well-site testing. To overcome these objections, a device was developed for use in the field which permits determination of the concentration of treating acid both quickly and accurately at the time of the acid treatment. Its purpose was three-fold, namely, to determine: (1) the concentration of the fresh treating acid, (2) the concentration of the spent acid returning from the well, and (3) the solubility of formation samples in treating acid. The device was designed to operate on the principle of the stoichiometric relation between the calcium carbonate—hydrochloric acid reaction and the carbon dioxide gas resulting from the reaction. By confining the carbon dioxide gas within a reaction cell of the type shown in Fig. 1, the pressure inside the cell is increased. Since the pressure is an indication of the quantity of carbon dioxide gas produced, it may be used to estimate the concentration of the acid, provided an excess of calcium carbonate is used. From information on the volume of the reaction cell, the volume of acid used, and the pressure and temperature of the gas after the completion of the reaction, the concentration of the treating acid may be computed. The reaction cell is essentially a pressure vessel equipped with a pressure gage, temperature indicator. pressure release valve, and a special sample holder. Plastic and metal construction makes the cell both rugged and acid-resistant. The sample holder is so designed that a sample of calcium carbonate (or sample of carbonate rock) can be dropped into the acid

Jan 1, 1956

By W. H. Bassett

A 10-year, sea-water, corrosion test of tubes of several copper alloys has shown that many alloys withstood attack by solution, pitting, and dezinkification; a 1-year, salt-spray test of sheet-metal specimens of the same composition showed the same results. THE late J. P. Sparrow, chief operating engineer of the New York Edison Co., carried out a series of practical tests on condenser tubes of several copper alloys and reported on the results to the Association of Edison Illuminating Companies at its meeting in' September, 1913. In the preparation of these tubes the senior author had the pleasure of cooperating. Copper-zinc alloys in the proportions of 60-40, 70-30, 80-20, 90-10, and Admiralty metal, which is in effect 70-30 with 1 per cent. of tin, were tried. Monel metal and several copper-nickel alloys, and 8, 5, and 3 per cent. aluminum bronze were also tried. At the time of this report, the aluminum bronze had been in service for 4 1/2 years and seemed to be giving especially good results but later it began to fail and showed no substantial improvement over Admiralty metal. Monel metal was unsatisfactory and the nickel alloys apparently did not give better service than the Admiralty alloy. Previous to the publication of the report, and after considerable discussion, it was agreed that a test where tubes of different kinds could be under laboratory observation would be advisable, so the apparatus described here was set up in The American Brass Co.'s Waterbury Laboratory. This was fitted with tubes of copper, brass, bronze, nickel silver, cupro-nickel and other alloys, and the test started Oct. 11, 1912. Salt water from East River, New York harbor, was barrelled and transported to the laboratory for the test. A fresh supply, completely replacing the water in service, was obtained at the end of each six months period.

Jan 1, 1925

By G. D. Gemmell

Effects of solid-sdutidn alloying with titanium, molybdenum, and tungsten at concentrations up to 10 pct on the strength of pure columbium at elevated temperatures (mainly 2000°F) have been investigated by means of creep-rupture, hot-tensile, and hot-hardness testing and recrystallization studies. ThIS paper presents some results from the initial part of a study of the effects of alloying on the high-temperature strength properties of columbium. The elevated-temperature strength characteristics of pure columbium were first studied. Binary alloys of columbium with titanium, molybdenum, and tungsten containing 1, 5, and 10 pct of the solute elements were chosen on the basis of their high melting points, their known solid solubility in columbium, and results of separate oxidation-resistance studies of columbium alloys. EXPERIMENTAL PROCEDURE All the materials used were of highest purity. A typical analysis of the columbium is shown in Table I. Compositions of the alloys are also given in Table I. To evaluate the strength properties of pure co-lumbium and the alloys at elevated temperatures, creep-rupture, hot-tensile, and hot-hardness testing was done on recrystallized material. To prepare the pure metal and the alloys for these tests, 1- 1b buttons were made in a water-cooled copper crucible, inert atmosphere, tungsten arc furnace. Tapered ingots, 3 in. long, were made from these buttons by a skull-casting technique and these were machined to 1/2 in. diam, swaged to 50 pct reduction (pure columbium at room temperature, alloys at lowest temperature possible without cracking, generally in range 1100" to 1800°F) and heated in vacuum (lo-' mm Hg) for 16 hr at 2550°F for re-crystallization and homogenization. The resulting grain diameter was 0.1 to 0.3 mm. The 10 pct Mo alloy casting was not successfully swaged at temperatures up to 1800°F without cracking and was not included in the test program. Creep-rupture testing was done at constant load in vacuum on cylindrical specimens of 0.16 in. diam, using Instron capsules. The pressure at test temperatures was less than 10-1 mm Hg. Hardneas readings taken on the test specimen before and after testing were used as a check on possible gaseous contamination. Hot tensile tests in vacuum on cylindrical specimens of 0.125 in. diam were also made with Instron equipment at a strain rate of 0.067 min.-l. Hot-hardness measurements were taken with a unit constructed at the Du Pont Experimental Station. The test piece, supported on an alumina anvil, and the molybdenum indenter shaft with sapphire tip is heated in a platinum-wound furnace. The load applied to the pyramid indenter is measured by strain gages attached to a proving ring located outside the hot zone. In the measurements reported here the load was I kg. The tester operates in a vacuum of about 10"5 mm Hg and is capable of temperatures up to 1400°C.

Jan 1, 1960

By C. E. Lesher

THE Disco* process for the production of low temperature coke and its immediate predecessor, the Wisner or Carbocite process have been described in the voluminous literature of low temperature carbonization.1-4 This paper will describe the development of the process from the first attempt at commercial operation by the American Gas and Electric Co. at Philo, Ohio,' in the 1920's to the successful operation in 1949 by the Disco Co., a division of the Pittsburgh Consolidation Coal Co., of the 1000-ton per day Disco plant near Pittsburgh, see Figs. 1-2. In the 1924 coal industry depression following the hectic post World War I expansion, the northern Appalachian, unionized bituminous coal fields were affected first and foremost, and Western Pennsylvania as hard as any. Competitive market pressure was heaviest on the lower grades of steam coals, notably those from the Panhandle district where ash and sulphur are inherently higher than in the same Pittsburgh coal bed to the east along the rivers. The firm structure of Panhandle coal while favoring the prepared sizes, depressed the usefulness and value of the finer sizes. Panhandle slack and nut slack were marketed with difficulty at consistent, and at times considerable, loss. Many solutions were suggested, and the Pittsburgh Coal Co. investigated all. Lower delivered prices through lower mine costs and more advantageous freight rates were obvious goals, but equally obvious were the difficulties of self attainment of either in any substantial measure. Selling Btu's in pipes was abandoned as an idea after a thorough study of the economics of distribution of what was then, and is even now, the only developed continuous process of complete gasification of bituminous coal-producer gas. Although the coal company purchased huge blocks of electric power, it sold not a car of coal to the central power stations. Public utilities controlled the markets for electric current, and it was found that no matter at how low a cost current might be put on the bus bars by the coal company, distribution to its widely scattered coal mines made such an enterprise practically impossible. Consolidation of underground operations and a huge modernization program of mining operations in the 1920's were but preparation for the introduction of mechanical cleaning of the coal for market, particularly the smaller sizes of steam, gas, and by-

Jan 1, 1952

By J. P. Heller, H. B. Bradley, A. S. Odeh

A potentiometric model technique is presented for determining the areal sweep efficiency of a five-spot well pattern, at and beyond breakthrough. A sharp interface between displaced and displacing fluids is assumed. Although the prototype svstem is referred to as a waterflood operation, obvious changes in the notation and computations will adapt the results to other displacement processes. The results of the study include the following. 1. Areal sweep efficiencies for a five-spot well pattern, at and beyond breakthrough, for mobility ratios (displacing to displaced fluid) of 4:1, 2:1, 1:1 and 1:4. 2. Extension of potentiometric analysis to the investigation of the areal sweep efficiency beyond breakthrough in a five-spot pattern by the application of conformal mapping and conductive-solid models. 3. The use of layers of conductive fabric in representing mobility ratio changes in potentiometric models. 4. The development of a probe mechanism for probing conductive solids. The results obtained by conductive-cloth models agree with earlier areal sweep efficiencies at breakthrough obtained by Aronofsky and Ramey 1 on the potentiometric analyzer using electrolytic-tank models. Results beyond breakthrough differ from those obtained by the X-Ray Shadowgraph technique. Data from this study show that, for mobility ratios greater than one, water cut rises rapidly as fluid is produced after breakthrough. However, for mobility ratios smaller than one, a large increase in area swept resulted with only a small increase in water cut. INTRODUCTION In calculating reservoir performance of waterflood-ing operations and other fluid-injection programs, it is necesssary to estimate the areal sweep efficiency * before and after injected-fluid breakthrough into production wells. Influence of mobility ratio on oil-production history, before and after breakthrough for a five-spot well pattern, has been studied by X-Ray Shadowgraph techniques 2-5 and by gelatin models.6 In none of these investigations was the transition zone controlled experimentally. Steady-state anaiog techniques assume that a vertical and discrete interface exists between the displacing and displaced phase. Thus, when using a potentiometric analysis, it is assumed that no transition zone exists. To determine the areal sweep efficiency beyond breakthrough for a five-spot well pattern using the potentiometric analyzer, four principal problems had to be resolved. These were the following. 1. The laborious method of representing changes in mobility ratio in electrolytic tanks by means of contoured wooden blocks. 2. Vapcrization of the electrolyte solution during the study causing concentration changes and, thereby, variable conductivity. 3. The scale-limitation problem 7 that is accentuated by abrupt eiectrolyte depth changes. 4. A wellbore geometry problem. EXPERIhlENTAL EQUIPMENT AND PROCEDURES CONDUCTIVE-SOLID MODEL The theory, equipment and procedural techniques of the electrolytic-tank potentiometric model have been treaced excellently by Lee8 and by Muskat.9 By the use of a conductive solid to represent the fluid conductivity of the porous media, the need for contouring wooden blocks to represent mobility ratio was eliminated. It was found that a carbon-black coated fabric, Uskon D-16,** could be employed as a fairly uniform conductive media. This material, when stacked in appropriate layers and pressed together, can be used to represent changes in mo-

By Jan Law

Problems of oil recovery are attacked from the approaches dictated by the two strikingly dissimilar complexes that comprise an oil reservoir—the fluid complex and the interstitial complex. Knowledge of the fluid complex, due to labors in the fields of fluid mechanics and physical chemistry, has far outdistanced knowledge of the interstitial characteristics of the sand complex. This paper is concerned with the latter and applies the technique of statistics to petrographic facts—namely, porosity and permeability—dealing with what might be called petrometry. Statisticians have long worked within the problem of reconstruction of a universe oi variables by means of samples that comprise a small percentage of the universe from which the samples were drawn. Core-analysis data comply with the requisite of random sampling as stipulated by theoretical statistics. A basic concept of statistics employs t.he following substitution: 1. The results of sampling are arranged as a frequency distribution. 2. The observed frequency distribution is compared with a mathematically precise distribution. 3. If a sufficiently good agreement is found between the two, the precise distribution is substituted in all subsequent operations involving characteristics of the sampled material. This mathematically precise distribution is also known as the normal curve, curve of error, the probability, the Gaussian, and the bell-shaped curve and is describable with but two figures. Further, these two figures, the arithmetic average and the standard deviation, are subject to mathematical manipulation. This paper demonstrates that, in some cases in the Dominguez field of Southern California, if sufficient core-analysis samples are taken over not too great a thickness of sediments, the resultant permeability and porosity assemblages give satisfactory agreement with ilormal curves. It is shown that the indications are strong that oil wells wherein a satisfactory agreement is found are predictable as to productivity. Since the predictions are made by employing the laws of chance that are operative within sedimentation, it follows that the mechanism by which the predictions were made is a basic concept of reservoir mechanics. Therefore, tentative examples are given of the application of normal curves to the solution of problems of primary and secondary recovery. Nature of Permeability Frequency Distributions Core-analysis data are made available as a tabulated depth vs. permeability profile. The nature of the distribution of permeability values within a given strati-graphic interval may be approximated from an array constructed with samples plotted in the order of their appearance with depth (accession number) against their permeability value in millidarcys. A wide variation in the nature of the distribution of K (permeability) values for

Jan 1, 1944

By Jan Law

Problems of oil recovery are attacked from the approaches dictated by the two strikingly dissimilar complexes that comprise an oil reservoir—the fluid complex and the interstitial complex. Knowledge of the fluid complex, due to labors in the fields of fluid mechanics and physical chemistry, has far outdistanced knowledge of the interstitial characteristics of the sand complex. This paper is concerned with the latter and applies the technique of statistics to petrographic facts—namely, porosity and permeability—dealing with what might be called petrometry. Statisticians have long worked within the problem of reconstruction of a universe oi variables by means of samples that comprise a small percentage of the universe from which the samples were drawn. Core-analysis data comply with the requisite of random sampling as stipulated by theoretical statistics. A basic concept of statistics employs t.he following substitution: 1. The results of sampling are arranged as a frequency distribution. 2. The observed frequency distribution is compared with a mathematically precise distribution. 3. If a sufficiently good agreement is found between the two, the precise distribution is substituted in all subsequent operations involving characteristics of the sampled material. This mathematically precise distribution is also known as the normal curve, curve of error, the probability, the Gaussian, and the bell-shaped curve and is describable with but two figures. Further, these two figures, the arithmetic average and the standard deviation, are subject to mathematical manipulation. This paper demonstrates that, in some cases in the Dominguez field of Southern California, if sufficient core-analysis samples are taken over not too great a thickness of sediments, the resultant permeability and porosity assemblages give satisfactory agreement with ilormal curves. It is shown that the indications are strong that oil wells wherein a satisfactory agreement is found are predictable as to productivity. Since the predictions are made by employing the laws of chance that are operative within sedimentation, it follows that the mechanism by which the predictions were made is a basic concept of reservoir mechanics. Therefore, tentative examples are given of the application of normal curves to the solution of problems of primary and secondary recovery. Nature of Permeability Frequency Distributions Core-analysis data are made available as a tabulated depth vs. permeability profile. The nature of the distribution of permeability values within a given strati-graphic interval may be approximated from an array constructed with samples plotted in the order of their appearance with depth (accession number) against their permeability value in millidarcys. A wide variation in the nature of the distribution of K (permeability) values for

Jan 1, 1944

By J. T. McGrath, G. B. Craig

Tensile tests on aluminum single crystals, grown from the melt, revealed that the yield stress of these crystals was raised as the amount of striation substructure was increased. The number of striation-type boundaries was varied by changing the rate of growth of the crystals. The results are interpreted in terns of a blockage of dislocation movement by striation boundaries. IMPERFECTIONS are known to have a large effect on the mechanical properties of metals. Teghtsoonian and Chalmers 1 studied a block or striation-type substructure in tin and found that the formation of the striations depended upon rate of crystal growth and orientation. They found that the angular misorienta-tion between neighboring striations varied between 15 min and 5 deg. Atwater and chalmers2 investigated striations in tin and lead, and found that purity was another factor which influenced their formation. There was a limiting purity above which the striations were straight and regular. There is little information in the literature concerning how substructures in melt-grown crystals affect strength. washburn3 introduced small-angle boundaries into zinc by a shear process and found a subsequent increase in yield stress which he attributed to the presence of these boundaries. Lauriente and pond4 found the critical resolved shear stress in aluminium crystals grown from the melt, to increase with etch pit density. The etch pits were used as an indication of growth imperfections. In Hibbard's5 work on lineage structure in copper crystals grown from the melt, he tested one crystal containing interlineage boundaries, and found a 50 pct increase in the critical resolved shear stress. Fleischer and Chalmers6, in a recent paper, mention briefly that, in the production of aluminium crystals from the melt when the growth rate was raised from 1.2 to 18 cm per hr, the yield stress increased 50 pct. They felt that the increase in yield stress with rate of growth might be attributed to a higher concentration of impurities in the gage length and also might be affected by the increased number of small-angle boundaries (striations). The present investigation was undertaken to determine the effect of the striation substructure on the strength of aluminum single crystals. EXPERIMENTAL PROCEDURE Aluminum single crystals of 99.9992 purity were grown from the melt using a technique described by Chalmers.7 The growth rate was varied from 0.6 to 20 mm per min, thus producing crystals with varying numbers of striation boundaries. To avoid prior deformation, the crystals were chemically cut to the desired length with a saturated solution of cupric chloride. They were then annealed at 580°C for 24 hr and allowed to cool slowly in the furnace. Finally, the specimens were electropolished using an electrolyte of 5 parts ethyl alcohol and 1 part perchloric acid. Each specimen was approximately 5 in. in length and 0.125 sq in. in cross section. The average orientations of the 5 series of crystals studied are shown on the stereographic projection of Fig. 1. The crystals were strained approximately 2 pct in a soft tensile machine. The strain sensitivity was 3.6 x 10-4 cm over a 5-cm gage length.

Jan 1, 1960

By W. M. Yim

Experimental results are presented which indicate that transverse striations in horizontal zone-leveled Bi-Sb alloy crystals are due to irregular growth rate resulting from thermal fluctuations in the melt (Iring gowth. Thc thermal fluctutations arose from two different sources. The first type was brought about by periodic fluctuations in the furnace temperature. The second type can be attributed to turbulent therrrol conlcclion in the trzelt near the solid-liquid inteyace. Tile arrzplitlcde ond fvequency of the tetiperaticre fluctlrations vesultity from llle lhevnal con1,ecrrell. The striation spacings in Lhe crystals covvelale well with the periodicity 0.f the tempevature flueluatiors. Altliough the strialiors represenl corrlpositiozul inhoiHogeneity oh a rzicroscule, less than f.z cil. be1 S6 in Best's as deterrirzed by electron-pro be chalq'sis, the slriations roerre fbund to ILUL' no rrleusuanble effect on electical vesistirity rwr on weak field macgnetoresistance of. the Bi-Sb a1lu.y in the ternpevutue ),unge 4.Polo 300°K. DURING the course of an investigation on the horizontal growth of semimetals,' it was found that crystals of Bi-Sb alloys contained many closely spaced parallel arrays of striations. These striations occurred perpendicular to the growth direction and parallel to the solid-liquid interface. We shall refer to them as transverse striations, or just striations'', to distinguish them from lineage substructures or longitudinal striations which form parallel to the growth direction and have been known to be associated with cellular structures.' Similar transverse striations have been reported previously to occur in other materials prepared by horizontal growth: metals,4 semiconductors,5 as well as their alls. - Various methods of crystal preparation have apparently little effect on the occurrence of the transverse striations. They form whether the crystals were grown by the vertical Czochralski technique, withe1' or without'3- rotation, or by the horizontal zoning methd.- Thus, the transverse striations are not limited to any one class of materials, nor to any particular method of preparation. It is likely, therefore, that all of the observed transverse striations may have some common cause. Previously, workers agreed that periodic changes in the growth rate bring about the striations. However, no agreement exists as to the origin of the growth-rate fluctuations. Some attributed the discontinuous growth to a purely external cause, such as fluctuations in the furnace temperature, jerky motions in the crystal pulling mechanism, or a nonsymmetrical temperature distribution in the melt (in the case of crystals grown by the Czochralski technique with rtation). Others looked for the cause in some fundamental property of the growth process itself. For instance, a certain degree of supercooling is required to initiate growth from the melt. But, with further growth, the degree of supercooling decreases because of the liberation of the heat of solidification at the solid-liquid interface. Thus, crystal growth would be brought to a halt until sufficient supercooling is resotred and the cycle begins again.3'11 According to this model, periodic fluctuations in the melt temperature should exist at the solid-liquid interface. Since the periodic fluctuations in growth rate would result in changes in the segregation coefficient of solute atoms, crystals containing the transverse striations may, in some cases, show a periodic impurity fluctuation along the length, resulting in a degradation of electrical properties. The resistivity striations in doped germanium'9-10 or lnsbB are well-known examples of this microsegregation. The present work was undertaken to explain the exact origin of the transverse striations, and to assess the extent of their effect on chemical homogeneity as well as on electrical properties of Bi-Sb alloy crystals. Results from our previous study of the crystal growth of Bi-Sb alloys1 indicated that the transverse striations may arise from the temperature fluctuations in the melt during growth. This paper will show that the melt temperature fluctuations are indeed responsible for the occurrence of the transverse striations. I) EXPERIMENTAL Although the transverse striations have been observed in all slow-grown Bi-Sb alloys across the entire compositional range, we selected a composition, Big3Sbs, for the present study in view of the extensive data available on the crystal growth of this alloy from a previous study.' High-purity bismuth and antimony, both a 6-nine grade by the manufacturer's emission spectrographic analysis, were used throughout. Independent mass-spectrographic analysis showed, however, that the starting materials were more nearly a 5-nine grade. each containing metallic impurities of approximately 10 ppm atomic. In zone-leveled Big5Sb5 alloys, the total metallic-impurity content was slightly lower, about 7 ppm atomic, indicating that some degree of purification was achieved during the growth. None of the electrically active impurities, such as tin and lead (acceptors) and tellurium and selenium (donors), were present in significant quantity in undoped Bi95Sb5. Typical analysis of the undoped Bi95Sb5 alloy is shown in Table I. Nonmetallic impurities, such as carbon and oxygen, were detected, sometimes as much as 100 ppm, in both the starting materials and the zone-leveled alloys: but the data were only qualitative. Temperature fluctuations in the melt were monitored over 1 or more days by means of a 5-mil chromel-

Jan 1, 1967

By A. S. Michaels, R. S. Timmins

A study of the effect upon oil recovery from an un-consolidated porous medium of chromatographic transport of selected reverse-wetting additives during water displacement is described. Flow tests were performed on hydrocarbon oil-saturated sand columns (containing connate water) into which small volumes of short-chain aliphatic amine solutions were introduced during water flooding. Concurrently, meusurements of oil-silica contact angles, oil-water interfacial tensions and oil-water distribution coefficients were measured us a function of additive concentration. Certain treatments were found to cause a slight reduction in oil recovery, while others produced a significant increase (up to 50 per cent of the normtzl irreducible rninimum oil saturation). Recovery eficiency was correlated most satisfactorily with the maximum degree of reverse wetting produced during additive transport; conditions which resulted in only mild oil wettability of the sand reduced recovery, while those favoring strong oil wetting increased recovery. A mechanism of reverse-wetting additive action during chromatographic transport is developed which ascribes the results to transient changes in oil-solid contact angle during flow, with consequent release of oil trapped by capillary forces. Implications of these observations with regard to improved waterflood efficiencies are discussed. INTRODUCTION The need for finding improved methods of oil production is amply illustrated by the large volume of oil considered economically unrecoverable by existing production practice. Water flooding has long been an excellent method of secondary recovery. However, even in those areas of a formation which are well swept by a water flood, 20 per cent or more of the oil remains trapped within the formation and is not recovered. This trapping of oil within the pores of the rock structure results primarily from interfacial forces. If these interfacial forces were altered, it is possible that the trapped oil could be released and recovered. The addition of surface-active agents to a water flood to alter the interfacial properties of the oil-water-solid system has received considerable attention as a method of increasing oil recovery. Studies of surfactant treatment have yielded varied and, in some cases, apparently conflicting results. Increased oil recovery using surface-active agents has been reported by a number of investigators. Others have found that use of surfactants in a water flood either has no effect upon oil recovery or decreases it. Since surface-active agents tend to alter the formation wettability and oil-water interfacial tension simultaneously, several investigators have tried to determine the role these two factors play in oil recovery. Data have been presented which indicate that the most desirable condition for the solid surface is strongly water-wet. Other results indicate that, although breakthrough recovery may be less, the greatest ultimate recovery is obtained when neutral wettability prevails.", " The desirability of low interfacial tension seems to depend upon the wettability of the formation. Reports of higher recoveries, when the interfacial tension is high in a water-wet system and low in an oil-wet system, are at odds with reports of increased recovery in water-wet systems when surfactants which decrease the interfacial tension are added to the water flood. A review of previous work studying the effects of using surface-active agents in a water flood shows that these agents produce widely different effects and that opinions as to the role of the various interfacial properties are diverse. The consensus, however, is that the interfacial properties are quite important in the displacement of oil from a porous medium by water. Even in those investigations where appreciable increases in oil recovery resulted from treatment with a surface-active agent, economic considerations generally made practical application of the treatment unattractive because surfactants tend to be adsorbed within the formation. This adsorption would necessitate using large quantities of surfactant if all of the flood water were treated to contain a given surfactant concentration, even if this concentration were quite low. Preston and Calhoun suggested that the principles of chromatography could be applied to the use of surface-active agents as a means of increasing oil recovery. A small volume of surface-active material is injec-

By E. B. Snyder, H. M. Kraner

This paper shows that volume stability, low porosity and decreased pyroplasticity are desirable for blast-furnace linings, partitularly for the hearth. It shows further that a hot load test is a valuable means of testing the fusion or softening behavior of a refractory at operating temperatures. The effect of carbon monoxide on commercia1 blast-furnace refractories in their as-received condition and after refiring is reported, showing that many commercial blast-furnace refractories disintegrate badly but that refiring decreases the effect and certain special refractories are now available which are almost free of the tendency. Factors Affecting Choice of ._ Refractories If one were to depend entirely upon experience or trial in the selection of clay refractories, the solution of a problem would be a slow process. Furnace campaigns are so long and attended by so many variables that it is difficult to draw fine distinctions within a reasonable period of time in regard to the quality of refractories used. It could be said, of course, that if service results do not yield the proper information for intelligent choice, there is no difference in the quality of brick being considered, but this is not necessarily true. Conventional ceramic tests are designed to give the ceramic engineer information as to the refractoriness and firing tempera- . ture, which he in turn internrets in terms of volume stability, ability to withstand load at high temperature (pyroplasticity), permeability, chemical stability and re-. sistance to the action of slag. In most refractory applications . several of these factors are involved. In a particular instance, one requirement may be predominant, while in others some other factors may be of primary importance. In this country, clay refractories are generally made from mixtures of plastic and flint fire clays. The process of firing a clay refractory is one of slowly melting the constituents, and during this operation its porosity is gradually reduced. The process is arrested, of course, in its incipient Stages and the Progress is determined by measuring slight changes in porosity, volume, bulk gravity, etc., that have taken place. Often the temperatures to which clay refractories are exposed in service are higher than those employed in their firing. However, if the manufacturer were to fire them at such high temperatures the brick would distort. Therefore it would be difficult for the manufacturer to fire all of his clay refractories to temperatures at which they are to be used, although in many cases it would be desirable from the user's point of view if he would do so. The porosity of clay refractories decreases by firing, to a minimum limit, after which a further increase in the temperature causes expansion in certain clay constituents and bloating in others. Both may occur in the same refractory containing two such clays.

Jan 1, 1944

By H. M. Kraner, E. B. Snyder

This paper shows that volume stability, low porosity and decreased pyroplasticity are desirable for blast-furnace linings, partitularly for the hearth. It shows further that a hot load test is a valuable means of testing the fusion or softening behavior of a refractory at operating temperatures. The effect of carbon monoxide on commercia1 blast-furnace refractories in their as-received condition and after refiring is reported, showing that many commercial blast-furnace refractories disintegrate badly but that refiring decreases the effect and certain special refractories are now available which are almost free of the tendency. Factors Affecting Choice of ._ Refractories If one were to depend entirely upon experience or trial in the selection of clay refractories, the solution of a problem would be a slow process. Furnace campaigns are so long and attended by so many variables that it is difficult to draw fine distinctions within a reasonable period of time in regard to the quality of refractories used. It could be said, of course, that if service results do not yield the proper information for intelligent choice, there is no difference in the quality of brick being considered, but this is not necessarily true. Conventional ceramic tests are designed to give the ceramic engineer information as to the refractoriness and firing tempera- . ture, which he in turn internrets in terms of volume stability, ability to withstand load at high temperature (pyroplasticity), permeability, chemical stability and re-. sistance to the action of slag. In most refractory applications . several of these factors are involved. In a particular instance, one requirement may be predominant, while in others some other factors may be of primary importance. In this country, clay refractories are generally made from mixtures of plastic and flint fire clays. The process of firing a clay refractory is one of slowly melting the constituents, and during this operation its porosity is gradually reduced. The process is arrested, of course, in its incipient Stages and the Progress is determined by measuring slight changes in porosity, volume, bulk gravity, etc., that have taken place. Often the temperatures to which clay refractories are exposed in service are higher than those employed in their firing. However, if the manufacturer were to fire them at such high temperatures the brick would distort. Therefore it would be difficult for the manufacturer to fire all of his clay refractories to temperatures at which they are to be used, although in many cases it would be desirable from the user's point of view if he would do so. The porosity of clay refractories decreases by firing, to a minimum limit, after which a further increase in the temperature causes expansion in certain clay constituents and bloating in others. Both may occur in the same refractory containing two such clays.

Jan 1, 1944

By E. N. Aqua, C. M. Owens

The microstructure in cold-rolled Zircaloy-4 sheet has been characterized by transmission electron microscopy and X-ray diffraction line-broadening techniques. The rate of work hardening is measured in terms of microstrains, particle sizes, micro hardness, the tensile yield strength. The tensile yield strength of Prestrained (less than 10 pet) Zircaloy-4 sheet is found to be a linear function of the square root of the dislocation density, us predicted by work-hardening theories. ZIRCALOY is one of the most important structural alloys for nuclear reactor applications.''2 In order to understand the effects of the nuclear environment on Zircaloy structural members, the preirradiation microstructure must be characterized. This report will describe the substructure existing in cold-rolled Zircaloy-4 sheet as observed by electron microscopy and by X-ray diffractometry. I) EXPERIMENTAL PROCEDURE Commercial Zircaloy-4 strip was cold-rolled and annealed in argon at 760°C for 1 hr. The annealed sheet was again cold-rolled to a maximum of 50 pct reduction in thickness with segments of the strip being retained after 2.5, 5, 10, and 20 pct reductions. One-inch-square portions were chemically polished (50 parts HNO3, 50 parts H2O, 10 parts HF) and mounted onto lucite blocks using double-sided tape to prevent bending during handling. Thin foils suitable for transmission electron microscopy were prepared from each of the sheet samples. The sheets were mechanically polished through 600-grit paper to a 3 to 4 mil thickness and were chemically polished by immersion for 1 to 2 min in a solution containing: 50 parts HNO3, 50 parts H2O, and 10 parts HF, and rinsed in distilled water. The final metallographic procedure was to electropolish for less than 10 sec with an electrolyte of 10 parts perchloric acid and 90 parts glacial acetic acid, at 20 v, at room temperature using stainless-steel point cathodes and a vigorous stirring action. These foils were examined in a Philips EM 200 electron microscope using a 100-kv accelerating voltage.

Jan 1, 1968

By G. Y. Chin, M. T. Dolan, W. L. Mammel

In the case of plastic deformation by slip, von Mises&apos; showed that an arbitrary shape change of a crystal generally requires the activation of five independent slip systems. The selection of the five active systems was worked out by Taylor ,&apos; who hypothesized that, among all combinations of equivalent slip systems which are capable of accommodating a given imposed strain, the active combination is that one for which the sum of the absolute values of the glide shears is a minimum. Taylor analyzed the case of {lll}( 110) slip for fcc metals and applied the analysis to crystals undergoing axisymmetric flow, which approximates the shape change of an embedded grain in a polycrystalline aggregate deformed in tension (or compression). For the twelve equivalent (111) (110) slip systems, there are 384 independent combinations of five slip systems that satisfy the imposed strain.&apos; Taylor laboriously calculated the value of M = ZjIyj /E for each combination (although some were missed) and obtained the minimum M, hence the active combination, for a number of axial orientations distributed throughout the stereographic triangle. (yj is shear from slip on the th system and e is the tensile strain). Detailed contours of constant minimum M were recently obtained by Hosford and Backofen using a simplified but equivalent Bishop and ill&apos; analysis. Due to the numerous combinations of slip systems involved in the calculations, however, the full potential of the powerful Taylor analysis has not been exploited. For this reason, we have recently utilized techniques of linear programming to obtain solutions of the Taylor analysis for axisymmetric flow, for slip on {110)(< 111), {112)(111), and {123)(111) systems as well as mixed slip composed of these three systems. These slip modes are of obvious importance in the deformation of bcc crystals. Some of the salient results are summarized below. 1) Stress-Strain Data for Polycrystal. The value of M averaged over all axial orientations is the ratio of the tensile flow strength of a randomly oriented aggregate to the critical resolved shear stress for slip. This value enters importantly in theoretical deductions of the polycrystalline stress-strain curve from single-crystal data.2&apos;3&apos;5 Table I lists the values of Ma,, for the several cases of slip, as obtained by the present computer work. 2) Texture Hardening. Since the value of M depends on the axial orientation, the (tensile) flow strength of a specimen may be increased through texture control.&apos; An example of the computer results is shown in Fig. 1, where contours of minimum M have been computer-plotted for the case of mixed slip on {110}(111), {112)(111),and {123}(11 1) systems. It may be seen that, under axisymmetric flow, wires of (111) and (110) axial orientations are 50 pct stronger than those oriented at (100) .

Jan 1, 1968

By L. Burris, G. A. Bennett, P. A. Nelson

Staznless steels ave rrzuch less seuel-ely attacketl by zinc lapov than by molten zinc systems. To determine the applicubility of stainless steels fov equipment items which would be exposed only to zinc vapor, the corvosion resistance of several stainless steels to zinc vapor was investigated in 500-hr- exposuves at 900° C. Two austenilic stainless steels, Types 304 and 3-17, suffered severe intergranular attack. Loss of nickel from these steels and micro-probe crnalyses indicated the probable formation of low-melting zinc-rich phases. Good vesistance to attack by zinc vapor, as determined by metallo-9-rpaphic excr)rtination and physical testing, Loas exhibited by Type 405 stainless steel, a jevvitic steel. Type 440C stainless steel, a tnartensitic steel, although suffering considevable loss in weight, was not structurally weakened. At Argonne National Laboratory liquid zinc and zinc-rich alloys are being employed as solvent media in pyrometallurgical processes under development for recovering and purifying discharged reactor-fuel materials.&apos; Because of the high solubility of most metals in liquid zinc,&apos; there are few metals which can serve as container materials for liquid zinc at temperatures much above the melting point. The poor corrosion resistance of the common metals and alloys to molten zinc has been discussed by Eldred.3 DeKany, Lavendel, and Burris4 tested some of the less-common alloys of the nonrefractory metals and found that they also have poor resistance to attack by liquid zinc and Zn-Mg solutions. Of the metallic materials, only some of the refractory metals such as tantalum, tungsten, and molybdenum and their alloys have shown resistance to attack by liquid zinc.4-7 In the process-development work at Argonne National Laboratory, tantalum and tungsten vessels have been used to hold liquid-zinc alloys. These vessels are housed in stainless-steel equipment, principally to permit maintenance of an inert atmosphere and operation at various pressures. In this experimental work, it has often been observed that Type 304 stainless steel suffers little attack by zinc vapor at temperatures up to about 800 °C. In contrast, severe attack occurs in areas where zinc condenses as a liquid. The extent of attack by zinc vapor on several stainless steels was investigated because there are possible useful applications of stainless steel for equipment items which would be exposed only to attack by zinc vapor. These applications include, for example, housings around processing equipment as indicated above and vapor lines leading from zinc stillpots or retorts to condensers. EXPERIMENTAL EQUIPMENT AND PROCEDURE The experimental procedure consisted in exposing stainless-steel test coupons to static zinc vapor for 500 hr at a temperature of about 900°C. The apparatus, shown in Fig. 1, consisted of a 12-in.-long closed tantalum tube jacketed in Type 304 stainless steel to prevent oxidation of the tantalum. A Zn-10 wtpct Mg* alloy charge of 293 g in the bottom of the

Jan 1, 1965

By D. L. Wood, J. H. Westbrook

The tensile behaviors of the CsCl structure compound AgMg are extensively documented in terms of strain, strain rate, temperature, composition, and metallurgical processing treatment. The observations lend themselves to presentation in terns of three regimes of deformation behavior; 1) low temperatures where deformation is primarily by slip; 2) intermediate temperatures where the deformation mode is also slip but with the detailed behavior dominated by dislocation interactions with solute atoms; 3) high temperatures where defomation is primarily by diffusion controlled processes. Of all the material groups of potential interest as high-temperature structural materials, the inter-metallics have been the least studied, particularly with respect to their mechanical behavior. Moreover, the application and processing of intermetallics for uses which exploit their often unique physical properties have been impeded by a lack of understanding of their mechanical properties. Previous work in this area* has been largely *For a recent review, see Westbrook.&apos; exploratory, aimed on the one hand at the direct empirical development of materials of engineering utility and ,on the other at identification of the important parameters affecting the mechanical behavior of inter metallics. As a consequence, there has not been available, heretofore—for any inter-metallic—data, sufficient in extent or precision to provide an adequate phenomenological description of the effects of metallurgical variables on deformation behavior. Such documentation is prerequisite to intelligent application or processing design and is also necessary for testing present and future theoretical analyses of mechanical behavior. It was therefore an objective of the present investigation to document the deformation behavior of a simple ordered intermetallic over as wide a range as possible of all the usual metallurgical variables. The compound AgMg was chosen as the subject of this investigation because it met all of a group of desired criteria, namely: 1) congruent but moderate melting point; 2) simple crystal structure; 3) ordered structure persisting to the melting point; 4) broad solubilities for the component elements. The first and last criteria were expected to aid in the preparation of homogeneous single-phase specimens: the second and third to help simplify the

Jan 1, 1962

By W. A. Backofen, G. Mayer

Single crystals of iron, copper, and a Cu-7 wt pct A1 alloy were pulled through conical dies to simulate the constraint in a polycrystalline aggregate undergoing axisymmetric reduction. With Taylor-type hardening, dependence of the drawing stress, od, on the Taylor orientation factor, M, is predictable from the polycrystal stress-strain curve; in particular, for a power-law relationship, it should follow that d log od/d log M = (1 + n). A first-order agreement with analysis was found in the data from iron. For copper, the implied n from the observed d log od/d l°g M was -0, while for Cu-7Al it was negative. The trend was in the direction of random polycrystal behavior. Thus the idea of hardening only in response to the amount of prior slip loses validity as stacking fault energy (SFE) is lowered. Two possible explanations have been suggested: as stacking fault ribbons are widened, barriers from dislocation reactions become increasingly effective in dispersing slip and reducing the orientation dependence of the total glide strain dm that appears in alternatively, or conjointly, the polyslip shear stress, 7, acquires an orientation dependence of a kind which has the same leveling effect on M. The problem of relating the strain hardening of polycrystalline material to that of an isolated single crystal is still largely unsolved. In a new experimental approach from recent work, single crystals of different orientations have been deformed under the constraints found in an aggregate while measuring their deformation resistance. Procedures have involved drawing cylindrical crystals through conical dies1 and compressing slab-shaped crystals in plane strain.2&apos;3 Predictions for the outcome of such experiments were made first by Taylor~ and later, in more general form, by Bishop and Hill.5&apos;6 Taylor&apos;s example was the axisymmetric extension of an fcc crystal slipping on the usual {111}(110) systems or, equivalently, a bcc crystal undergoing &apos;kestricted" slip on {110}(111). In his solution, the deformation work supplied was equated to that dissipated internally in slip on all active systems. With o the single applied tensile stress, dc the resulting axial strain, and dyT the total glide strain on systems operating at resolved shear stress, 7: The orientation dependence of M was found by minimizing dyT for each orientation while activating five independent systems, Fig. l(a).? The Bishop and Hill analysis, based on a principle of maximum work, leads to essentially the same conclusion; the need for at least five active systems is recognized in the finding that either six or eight are actually brought into operation. The mean value from the entire stereo-graphic triangle in either case is M - 3.06. More recently, Hutchinson8 made a Taylor-type analysis for pencil glide in a bcc structure, from which piehlerg prepared Fig. l(b) as the counterpart in Fig. l(a); here M = 2.75. The obvious weakness in such analyses is the indifference to slip-system interactions. A condition of what might be termed "independent"

Jan 1, 1969