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By Frederic L. Kadey

Perlite, as a volcanic glass, has been recognized since the Third Century, B.C. (Langford, 1978). The precise details of discovery often become lost in antiquity, and the variations among the stories pertaining to the more recent discovery of perlite as a material of commerce are no exception. Credit in the United States is given to a dentist who, while experimenting with tooth enamels about 1941, discovered that perlite-the rock-intumesced when subjected to heat. At about the same time it is reported that the chief geologist of Silver and Barytes Ores Mining Co. attempted to put out a picnic bonfire on the shores of Milos Island, Greece by throwing beach sand on it. The ensuing pyrotechnic display immediately conjured up in that man's mind the possibility of a new use for the volcanic rock that constituted most of the island. Very little was done with this discovery either here or abroad until after World War II. Today the name perlite is applied to both the hydrated volcanic glass, generally of rhyolitic composition, and to the lightweight aggregate that is produced from the expansion of the glass after it has been crushed and sized. Petrologically, it is defined as a glassy rhyolite that has a pearly luster and concentric, onionskin parting. Occurrences of perlite are restricted to several Tertiary to Quaternary age rhyolitic belts that trend in a generally north-south direction around the world. Commercially suitable deposits generally occur as domes of several hundred feet in height, although glassy zones in welded ash-flow tuffs and others associated with dikes and sills also have been reported. Mining is by ripping and blasting from open pits. Because of weight considerations, perlite usually is shipped to the local market area for subsequent expanding. In the United States, New Mexico leads in production with Arizona, California, Nevada, Idaho, and Colorado following in approximately that order. The principal use for expanded perlite is as a lightweight insulating aggregate in cryogenics, in plaster, concrete, and in loose fill insulation. Expanded perlite is also used in horticultural applications, and after subsequent milling and classification, as a filter aid. The United States is the world's largest producer and consumer of perlite. Table 1 shows the world production of perlite and Table 2 shows the perlite mined, processed, expanded, and sold or used by producers in the United States. Geology Composition and Morphology Any discussion of perlite must take into consideration its dual nomenclature, for it is known by the same name as both the naturally occurring rock and, after processing and expansion, as the lightweight aggregate of commercial significance. In its naturally occurring form, perlite is a rhyolitic glass that contains from 2 to 5% combined water. While perlite also can occur as andesitic or dacitic glass, these latter types are of negligible commercial significance. Table 3 lists the chemical composition of a few typical perlites (Anderson, et al., 1956; Langford, 1979). What sets perlite of commercial significance apart from other volcanic glasses is the fact that under the proper conditions of preparation-crushing and sizing-it will, when rapidly introduced into a flame of sufficient temperature, expand or "pop." All of the elements of composition contribute to the expansibility of the rock. The role of the combined water, however, is the most significant because it is believed not only to produce a fluxing effect in the softening of the highly siliceous glass prior to expansion, but it is also responsible for the explosive force of expansion through volatilization during heating. The current theory of the origin of the water in perlite is now less con-

Jan 1, 1983

By Keith R. Bock, Norman Parlee, Albert M. Barloga

Coils of pure iron and iron-carbon alloy wire (0.05 to 0.80 pct C) and sufficient sulfur to saturate the solid phase were equilibrated in evacuated or argon filled tubes. After rapid cooling, and removal of the outside nonmetallic layer, the wires were analyzed for carbon and sulfur and the data used to construct an Fe-S binary and isotherms of the Fe-C-S ternary in the range 1149° to 1427°C. THE solid solubility of sulfur in steel is of interest in connection with such phenomena as hot shortness, burning, and so forth. "Burning," the more or less permanent damage that some steels suffer when heated for forging or rolling, has been shown to be related closely to the behavior of sulfur and less closely to carbon and oxygen.' Attempts to interpret burning phenomena in steels fail because of lack of data on the Fe-C-S and the more complex systems in this family. Rosenqvist and Dunicz 2 and Turkdogan, Ignatowicz, and pearson3 have largely elucidated the Fe-S diagram in the region of interest but no information on the Fe-C-S diagram in this region appears to be available in the literature. This paper deals with the elucidation of the Fe-C-S diagram in these interesting ranges. The method employed is different from those used by previous workers2'3 on the Fe-S system. EXPERIMENTAL METHOD Pure iron wires (Ferrovac E) or iron carbon alloy wires of 1 mm in diam were cleaned with acid and acetone, coiled, and placed in silica tubes (7 mm OD and 5 mm ID) previously closed at one end. Enough sulfur was added to assure saturation of the solid iron phase. The filled tubes were either simply evacuated and sealed, or filled with argon at a reduced pressure and sealed. The argon was required at the higher temperatures to prevent collapse of the tubes. The filled and sealed tubes were placed in the middle uniform temperature zone of a Globar tube furnace and equilibrated at temperatures ranging from 2100°F (1149°C) to 2720°F (1493°C). After equilibration the tubes were removed from the furnace and quenched in air or water, the form of quenching being found to have no effect on the results. The tubes were broken open and the coils were placed in a 1 : 1 HC1 solution to remove the sulfide-rich layer. The coils were then cut into small pieces and analyzed for sulfur and carbon. In the early stages of the investigation different equilibration times ranging up to 17 hr were tried and the cores of the wires were analyzed to test for saturation. One hour appeared to be sufficient to reach maximum sulfur content at 1454°C and 2 hr sufficient at 1149°C. The practice adopted was to use at least 3 hr at the higher temperatures and at least 5 hr at the lower temperatures. The iron-carbon alloy wires used were made by carburizing pure iron wire with carbon monoxide gas in a one inch diameter ceramic tube at about 1204°C. Differing carbon contents were obtained by allowing fairly large coils to react with the gas for varying lengths of time at a flow rate of 800 cc per min. The reacting times ranged from 15 min to 4 hr depending upon the amount of carbon desired. The furnaces used were controlled by means of Leeds and Northrup Speedomax Type H instruments with D.A.T. Control attachment. Thermocouples were calibrated against the melting points of gold and copper. The temperatures recorded appear to be accurate within i2.7OC. Starting with run No. 85 and continuing with the

Jan 1, 1962

By R. J. Blackwell, J. R. Rayne, J. R. Henderson, W. M. Terry, D. C. Lindley

This paper presents the results of a laboratory investigation of the efficiency of water-solvent mixtures in recovery of oil. These mixtures may have the high displacement efficiencies characteristic of solvent floods and the high sweep efficiencies characteristic of water floods. Thus, the water-solvent process may increase the number of reservoirs in which a miscible-type displacement can be used profitably. The experiments on the use of water-solvent mixtures for recovery of oil were conducted to find the general applicability of the process. These studies demonstrated that, in flowing through sands, water and solvent segregated into a solvent layer on the top and a water layer on the bottom rather than flowing through the sands as a uniform mixture. Calculations based on the simultaneous flow of the water and solvent in layers were used to predict the effective mobility of the mixtures and the optimum operation of the process in steeply dipping, homogeneous reservoirs. As most reservoirs are not suited for the operation of the process under ideal conditions, experimental studies were conducted with sand-packed models scaled to represent more realistic reservoirs. These studies included the effects on recovery of oil of rate of injection, viscosity of oil, variations of permeablity within a formation and variations in water-solvent ratio. For the range of con-ditions studied, higher recoveries of oil were obtained with water-solvent mixtures than with water or practical volumes of solvent alone. INTRODUCTION A group of intriguing—because of their great possibilities—new oil recovery methods at the disposal of the petroleum engineer are the miscible displacement processes. These processes (high-pressure gas drive, en-riched-gas drive and LPG bank driven by methane) displace all of the oil from the portions of the reservoir swept by the injection fluid. The key question confronting the engineer applying one of these techniques to a particular reservoir is, "What fraction of the reservoir can be swept by injection of a practical volume of solvent?"." Intensive laboratory studies have been made during the past several years in seeking answers to the question of the sweep efficiencies which can be expected in solvent floods.' - These studies provided the answer that low-viscosity, low-density solvents channel and by-pass oil in sands with no dip. In horizontal sands, solvent flooding becomes less efficient as the viscosity of the oil increases, the recovery of oil at solvent breakthrough decreases and larger volumes of solvent are required to achieve a given recovery. More efficient displacement of oil by solvent is observed under certain conditions in sands with dip.".' If the permeability and dip of the sand are sufficiently high, gravity segregation of low-density solvent injected updip can prevent channeling. At rates of depletion below a critical rate,"." no channeling occurs. Unfortunately, in many reservoirs, the critical rate is so low that production of oil at rates below this rate is not economically attractive. And at rates over four times the critical rate, channeling is almost as severe in sands with dip as in horizontal sands. These findings pointed out that, for solvent floods to be generally applicable in recovering oil from all types of reservoirs, new methods of improving their sweep efficiencies are needed. Simultaneous injection of water with the miscible fluid was suggested by Caudle and Dyes7 as a method for improving sweep efficiencies. They theorize that water flowing with the solvent would decrease the effective mobility of the solvent and cause it to contact more oil sand. If, indeed, the water and solvent flowed as a uniform mixture, the process should have the advantages of the high displacement efficiencies characteristic of miscible floods and the high sweep efficiencies of water floods. Thus, the method (at least in theory) would greatly increase the number of reservoirs in which miscible-type displacements would be feasible. A research program was conducted to probe the technical feasibility of the water-solvent process. It

By George R. St. Pierre, John Chipman

METALLURGISTS have been studying the chem-ical behavior of sulfur in steelmaking for many years in order to have a better control of the sulfur content of finished steel. During the refining period in the open hearth, molten steel is separated from a gas phase by molten slag. Chemical reactions occur principally at the slag-metal interface and at the slag-gas interface. A need for physical-chemical investigations of reactions between sulfur-bearing gases and steelmaking slags was recognized some time ago.'.' From the early work, it can be qualitatively concluded that increased sulfur content and low partial pressure of oxygen in the gas phase favor the passage of sulfur from gas to slag. Using radioactive sulfur S Koch and Fink' have demonstrated the rapid rate of exchange of sulfur between gas and slag in an open hearth furnace. Gurry and Darken and Darken and Shields (as reported by Derge and Marshall') have equilibrated lime-iron oxide slags with SO—O2 gas mixtures. The major conclusion from the reported results is that sulfur content increases with increasing lime content in lime-iron oxide slags equilibrated with a gas of high oxygen pressure (10-2). The data were interpreted as indicating the presence of SO, and S,O, ions. Richardson and Fincham' have conducted the most extensive experimental study of sulfur equilibria between gas and slag. Their results confirmed many of the conclusions drawn from calculations of Richardson" and Withers. Richardson and Fincham's data fitted very well into the sulfur scheme represented by the reactions 1/2 s2 (g) + (0) melt - 1/202(g)+ (S) melt [II 1/2 S, (g) + 3/2 O (g) + (0) melt - (SO,) melt. [2] At oxygen pressures greater than 10 to 10 they found that reaction Eq. 2 was predominant while reaction Eq. 1 was controlling at oxygen pressures less than 10." to 10.". The slag compositions and gas mixtures used in their investigations were different from those used in the present study. Wherever possible, comparison has been made between their results and these, and agreement is excellent. It is evident that the distribution of sulfur between slag and gas depends upon the oxygen pressure of the gas. In FeO slags, a change in oxygen pressure produces a change in ferric oxide content, and a knowledge of this equilibrium is a prerequisite to studies of sulfur distribution. The data are found in the work of Darken and Gurry" on the FeO system and the more recent experiments of Gurry and Darken" and of Larson and Chipman" on FeO slags containing lime and silica. The effect of oxygen pressure on the ratio Fe /(Fe" + Fe ), the so-called j-ratio, reported by these investigators will be used in interpreting the results which follow. Experimental Method The purpose of the experimental program was to determine the equilibrium sulfur content in slags exposed to gases of known oxygen and sulfur pres- sures. The slag compositions selected for study were from the lime-silica-iron oxide system. Additions of magnesia were made to some of the slags. Apparatus—The apparatus used by Larson and Chipman was modified slightly to accommodate the addition of SO2 to the gas mixtures. As in their work, slag samples of 0.5 to 2.0 g were held at temperature (lcc) in platinum crucibles under a steady stream of gas, 100 to 200 ml per min, for several hours and then rapidly lowered to the bottom of the furnace where they were quenched in mercury. Preparation and Analysis of Gas Mixtures—Mixtures of SO,-CO were prepared from Virginia Smelting Co. Extra Dry liquid SO, and Pure Co. CO,. After removing traces of water vapor with an-hydrone, the CO, was passed over graphite at 1200°C, at which temperature the conversion to

Jan 1, 1957

HIGH-GRADE manganese ore, from which manganese is obtained commercially, is not found in large quantities in any major steel-producing nation in the free world. The U. S. is a "have not" nation with respect to deposits of directly mineable high-grade manganese ore. Known resources of 48 pct Mn or better grade ore amount to less than 200,000 tons. In 1950 the U. S. steel industry consumed 1.8 million short tons of metallurgical grade manganese ore that contained about 800,000 tons of manganese. About 16 pct of the manganese content was lost in processing, so that about 650,000 tons, or 13 pounds per ton of steel actually entered into steel production. Under present practices use expands directly with steel output, and by 1975 the demand in both the U. S. and the rest of the free world is expected to be roughly 60 pet greater than in 1950. In peacetime about 80 pet of manganese consumption goes into steel production; high-manganese steel, dry cells, and chemicals account for the remainder. The manganese supply problem centers around high-grade ore for ferromanganese production. Use of ores containing less than 35 pet Mn sharply increase the costs of making ferromanganese. Use of ferro-manganese of grade below 70 pet in turn requires changes in steelmaking that increase steel cost. Under normal conditions the present small domestic production cannot be expected to increase. Major resources in the U. S. consist of 12 low-grade deposits. The cost of mining and treating these ores to extract a product as good as that yielded by imported ores is at least twice and in some cases more than four times the 1951 price of foreign ores delivered to the U. S. However, as long as trade relations and overseas shipping are not interrupted, deposits in India, Africa, and Brazil can meet steadily increasing demand at approximately present costs. Cost considerations indicate that the U. S. should continue to rely upon overseas sources for its peace-time supply, and that this situation is satisfactory. But, this does not take into account the question of how the U. S. will be able to meet its needs in war. Position of the Rest of the Free World In 1950, free world steel producers outside the United States, with a steel output of 70 million ingot tons, consumed about 1.3 million tons of metallurgical-grade ore. Their manganese ore demand, expected to increase directly with steel production, will by 1975 be about 2.3 million tons. Russia possesses over half the known manganese ore reserves of the world and is producing twice the tonnage of any other country. It supplied more than a third of the U. S. manganese requirements up to 1938 and again in 1948, but by 1950 Soviet manganese exports to the free world had virtually ceased. The free world's supply of manganese now comes mainly from India and Africa. Somewhat over 10 pet of U. S. imports came from Brazil and Cuba. Security Considerations In the event of war the U. S. might be substantially cut off from 90 pet of present sources. Reduction in manganese specifications might cut consumption by over 10 pet without seriously affecting steel quality. By elimination of losses in the production of ferromanganese savings as high as 10 pet might be possible. But, wartime manganese requirements cannot be met through conservation alone. To meet possible future emergencies the U. S. should continue its comprehensive security program for manganese, including stockpiling and research on the economic use of low-grade ore, domestic ores, the recovery of manganese from slag and the reduction of manganese requirements in steel production. If this work, including additional pilot plant operation is pursued vigorously, it should be possible in an emergency to get an adequate supply of manganese from domestic sources. The national stockpile then can be looked upon as a source of supply during the period of at least 2 years required to reach full-scale production from low-grade resources. Ferromanganese Smelting In comparison with smelting of pig iron, ferro-manganese smelting is a very wasteful process. Under present ferromanganese blast-furnace smelting practice, about 8 pet of the manganese in the furnace charge is lost to the slag, and roughly the same amount is lost to the stack gases; the total loss approaches 15 pct. Present practice is a compromise between excessive slag loss and excessive stack loss. In fact, it may be seriously questioned whether conventional blast furnace design is suitable for manganese smelting. U. S. Resources The known manganese deposits of the U. S. contain a total of 3500 million long tons of raw material and 75 million long tons of metallic manganese. More than 98 pct of this contained metal is in 12 large low-grade deposits of which the most important are those at Chamberlain, S. Dak; Cuyuna, Minn.; Aroostook County, Maine; and Artillery Peak, Ariz. Reserves of high-grade ore (48 pct Mn) amount to less than 200,000 tons. About 20 million tons of ore average over 15 pct Mn, and when grade is decreased to 10 pct Mn reserves amount to about 100 million long tons. If cut-off grade is decreased to 5 pet Mn, resources amount to 800 million long tons. Many of these low-grade ores may be beneficiated by flotation or other concentration methods. Pyrometallurgical Methods For smelting ferromanganese, it is essential to have an ore containing at least 50 pct manganese, with an Mn:Fe ratio of about 8:1. Direct smelting of 20 pct Mn concentrates is not promising. The only method that offers any promise involves two-step smelting.

Jan 1, 1952

By V. Koump, T. F. Perzak, R. H. Tien

A series of experiments were carried out in which the rates of propagation of the liquidus and the eutectic fronts Mere measured during essentially one-dimensional freezing of Al-Cu alloys. The dimensions of the ingots were 3 by 5 by 6 in. Three different alloys containing 0.1, 4.5, and 17 pct Cu were used in these experitments. For each alloy the rate of heat removal was varied to give a total jreezing time in the range 3 to 30 min. The results of these measurements cowlpared favorably with the theoretical model of freezing of binary alloys with time-dependent surface temperature. IN engineering analysis of solidification of commercia1 steels and nonferrous alloys it is a common practice to assume that an alloy freezes by propagation of an isothermal solidification front, i.e., essentially as a pure metal. In two recent theoretical investigations'j2 the present authors explored the possibility of a more realistic approach to the problem of solidification of alloys. In the proposed model the freezing of an alloy is assumed to take place by propagation of two isothermal fronts, i.e., the liquidus front and the solidus (or eutectic) front. The region between the two fronts contains both liquid and solid and is referred to as the solid-liquid region. The width and the solid content of the solid-liquid region vary with alloy type, solute concentration, and cooling rate. For a given alloy system, initial concentration of solute, and the mode of heat removal, the proposed model yields the temperature distribution within the solid skin, temperature, solid fraction, and concentration distributions with the solid-liquid region, and the rates of propagation of the liquidus and the solidus fronts. This model is obviously of considerable practical importance in engineering analysis of solidification processes, since it gives a more realistic estimate of skin strength during solidification and a better estimate of the total freezing time. Before the new model can be used with confidence, however, it is necessary to test this model experimentally. The experimental testing of the proposed model is a relatively simple matter since the effects to be measured are large and a relatively simple experiment will suffice. The theoretical model predicts, for example, that during freezing of an alloy containing substitutional type solute (negligible diffusion in the solid during freezing) the solid-liquid region occupies an appreciable portion of the ingot, even at low concentration of solute.' Another prediction of the theo- V. KOUMP, formerly with U. S. Steel Corp., is now with Research and Development Center, Systems and Process Division, Westinghouse Electric Corp., Pittsburgh, Pa. R. H. TlEN is Senior Scientist, Fundamental Research Laboratory, U. S. Steel Corp., Research Center, Monroe ville, Pa. T. F. PERZAK, formerly with U.S. Steel Corp., is now with Fiber Industries, Greenville, S. C. Manuscript submitted March 6, 1968. IMD retical model, easily verifiable by experiment, is that the rate of propagation of the solidus (or eutectic) front increases as the solidus front approaches the center of the slab. This prediction is contrary to well-known behavior of the solidification front during freezing of pure metals, where the rate of propagation of the solidification front decreases with time and freezing is completed at the lowest rate. A rather severe test of the proposed model is provided by comparison of theoretical predictions and experimental measurements of the effects of cooling rate and composition on the rates of propagation of the liquidus and the eutectic fronts. In order to test the soundness of the formulation and the method of solution of the problem of solidification of alloys a series of experiments were carried out in which the rates of propagation of the liquidus and the eutectic fronts were measured during essentially one-dimensional solidification of A1-Cu alloys. The A1-Cu system was chosen strictly as a matter of convenience. Three different alloys containing 0.1, 4.5, and 17 pct Cu were used in these experiments. For each alloy the rate of heat removal was varied to give the total freezing time in the range 3 to 30 min. The results of these measurements are compared with the predictions of the theoretical model of solidification of binary alloys, with time-dependent surface temperature.' Before the experiments described in this paper were undertaken, a serious attempt was made to utilize the measurements of previous investigators to test the theoretical model. In the course of this preliminary study a careful review was made of experiments of Pellini and coworkers3 and Doherty and Melf~rd.~ The measurements in Pellini's work were carried out using a steel containing at least four major components. Evaluation of the solid fraction-temperature relation for this steel (required in the theoretical model) is difficult and uncertain. Doherty and Melford, on the other hand, measured the solid fraction-temperature relation experimentally, but did not give sufficient data to explore the effects of composition and the cooling rates on solidification. Hence it was not possible to utilize these measurements to test our theoretical model. EXPERIMENTAL METHOD The experimental technique used in this investigation differs somewhat from the more conventional techniques employed in solidification studies. This technique was developed primarily to eliminate con-vective mixing in the molten metal caused by pouring of molten metal into the mold. In our experiments A1-Cu alloys were melted directly in the mold. The mold assembly used in solidification experiments is shown in Fig. 1. The mold was fabricated from *-in. stainless-steel sheet. The dimensions of

Jan 1, 1969

By S. H. Williston

IT not often that bore hole surveys can be checked by actual. civil engineering methods. A recent Arizona survey was checked by normal surveying methods and the comparison of the results should be of value to both oil and mining men. During the summer of 1948 the Phelps-Dodge Corporation, at its Copper Queen property near Bis-bee, Ariz., drilled a 1245 ft, 8 in. diarn, churn drillhole in a mineralized area and cased part of it, intending to use it to transfer mill tailings for stope fill. The hole, as frequently occurs, was not straight, and, in endeavoring to locate the bottom in the underground workings, they found no evidence of the hole at the underground coordinates directly below the surface location. The noise of the drilling tools was reasonably clear, but the direction of sound was uncertain. Preliminary tests with available equipment were not successful in locating the bottom of the hole. Because of the mineralized character of the area and the fact there was some casing in the hole, any magnetic method of well surveying would give results of doubtful value. Sperry-Sun gyroscopic well-surveying instruments were finally used to locate the bottom of the hole. These instruments consist of a gyroscope to determine azimuth and either a pendulum or bubble inclino-meter. A multiple shot camera photographs both instruments on a single film and superimposes the photograph of a watch. Coordination of depth with time at the surface makes it possible to select the corresponding picture for any depth. After making several runs of the empty instrument housing from the top of the hole to the bottom to make sure there were no obstructions in the hole, three surveys on wire line were completed during the afternoon. The three surveys, in which readings were taken at different points in the hole on each survey, were computed and gave the following locations of the bottom of the hole in relation to the surface collar: survey No. 1—24.92 N, 30.30 W; survey No. 2—24.24 N, 31.11 W; survey No. 3—26.54 N, 27.72 W. Then the data from the three surveys were combined into a single set of calculations which gave a location for the bottom of the hole: combined surveys—24.27 N, 30.16 W. (Fig. 1.) Immediately upon the determination of the coordinates at the bottom of the hole, a drift on the 1300 ft level was started toward the indicated loca- tion some 38 ft northwest of the coordinates of the surface location, The bottom of the hole was located within the drift round in which it was expected, and the transit survey run to the actual location of the hole indicated N 27.18, W 29.71. This shows a discrepancy between the well survey and the transit survey of 0.45 ft in the westerly direction and 2.91 ft in the northerly direction. All surveys, both gyroscopic and transit, fell well within the width of an ordinary drift. While this is satisfactory for almost any and all mining requirements, a theoretical examination was made as to reasons for the discrepancy. A study of the course of the hole indicates that considerable right turn or spiral existed, and in all probability the surveying instrument was pulled out of alignment while traversing the turn by approximately 0.05 ft at the top and another 0.05 ft in the opposite direction at the bottom of the instrument. If such an allowance were to be made, the survey calculations would almost exactly correspond with those determined by transit. This sort of discrepancy would be minimized by the use of stabilizing guides. It is unfortunate that physical laws probably effectively prevent the use of gyroscopic instruments in EX and AX diamond drill holes. The directive power of a gyroscope falls off inversely at some rate between the third power and the sixth power of the diameter. Present instruments can be run in casing 53/4 in. ID or over and might be adapted to somewhat smaller diameters, but the difficulty of reducing these diameters to 11/4 in. or 2 in. is almost insurmountable at the present time. Acknowledgment The author wishes to express his appreciation to the Phelps-Dodge Corporation for permission to publish this article, and to the Operating and Engineering Departments for their cooperation on the survey; also to Donald Hering, of the Sperry-Sun Well Surveying Co., who actually made the survey and calculated the results.

Jan 1, 1951

By S. H. Williston

IT not often that bore hole surveys can be checked by actual. civil engineering methods. A recent Arizona survey was checked by normal surveying methods and the comparison of the results should be of value to both oil and mining men. During the summer of 1948 the Phelps-Dodge Corporation, at its Copper Queen property near Bis-bee, Ariz., drilled a 1245 ft, 8 in. diarn, churn drillhole in a mineralized area and cased part of it, intending to use it to transfer mill tailings for stope fill. The hole, as frequently occurs, was not straight, and, in endeavoring to locate the bottom in the underground workings, they found no evidence of the hole at the underground coordinates directly below the surface location. The noise of the drilling tools was reasonably clear, but the direction of sound was uncertain. Preliminary tests with available equipment were not successful in locating the bottom of the hole. Because of the mineralized character of the area and the fact there was some casing in the hole, any magnetic method of well surveying would give results of doubtful value. Sperry-Sun gyroscopic well-surveying instruments were finally used to locate the bottom of the hole. These instruments consist of a gyroscope to determine azimuth and either a pendulum or bubble inclino-meter. A multiple shot camera photographs both instruments on a single film and superimposes the photograph of a watch. Coordination of depth with time at the surface makes it possible to select the corresponding picture for any depth. After making several runs of the empty instrument housing from the top of the hole to the bottom to make sure there were no obstructions in the hole, three surveys on wire line were completed during the afternoon. The three surveys, in which readings were taken at different points in the hole on each survey, were computed and gave the following locations of the bottom of the hole in relation to the surface collar: survey No. 1—24.92 N, 30.30 W; survey No. 2—24.24 N, 31.11 W; survey No. 3—26.54 N, 27.72 W. Then the data from the three surveys were combined into a single set of calculations which gave a location for the bottom of the hole: combined surveys—24.27 N, 30.16 W. (Fig. 1.) Immediately upon the determination of the coordinates at the bottom of the hole, a drift on the 1300 ft level was started toward the indicated loca- tion some 38 ft northwest of the coordinates of the surface location, The bottom of the hole was located within the drift round in which it was expected, and the transit survey run to the actual location of the hole indicated N 27.18, W 29.71. This shows a discrepancy between the well survey and the transit survey of 0.45 ft in the westerly direction and 2.91 ft in the northerly direction. All surveys, both gyroscopic and transit, fell well within the width of an ordinary drift. While this is satisfactory for almost any and all mining requirements, a theoretical examination was made as to reasons for the discrepancy. A study of the course of the hole indicates that considerable right turn or spiral existed, and in all probability the surveying instrument was pulled out of alignment while traversing the turn by approximately 0.05 ft at the top and another 0.05 ft in the opposite direction at the bottom of the instrument. If such an allowance were to be made, the survey calculations would almost exactly correspond with those determined by transit. This sort of discrepancy would be minimized by the use of stabilizing guides. It is unfortunate that physical laws probably effectively prevent the use of gyroscopic instruments in EX and AX diamond drill holes. The directive power of a gyroscope falls off inversely at some rate between the third power and the sixth power of the diameter. Present instruments can be run in casing 53/4 in. ID or over and might be adapted to somewhat smaller diameters, but the difficulty of reducing these diameters to 11/4 in. or 2 in. is almost insurmountable at the present time. Acknowledgment The author wishes to express his appreciation to the Phelps-Dodge Corporation for permission to publish this article, and to the Operating and Engineering Departments for their cooperation on the survey; also to Donald Hering, of the Sperry-Sun Well Surveying Co., who actually made the survey and calculated the results.

Jan 1, 1951

By Herman Dykstra, R. L. Parsons

A numerical method for solving partial differential equations in steady state fluid flow is described. This method, known as the "relaxation method," has two advantages over analytical methods: (1) practically any problem can be solved, and (2) a solution can be obtained quickly. A disadvautage is that the solution is not general. The method is applied to core analysis and relative permeability measurement to calculate constriction effects and to calculate the true pressure drop measured by a center tap in a Hassler type relative permeability apparatus. Further applications are suggested. INTRODUCTION Many problems in fluid flow cannot be solved analytically because of the nature of the boundary conditions. For many problems, however. an exact answer is not necessary because boundary conditions are not exactly defined or the parameters describing the porous medium are not accurately known. The relaxation method can be used to obtain an approximate answer easily and quickly for the flow of incompressible fluids in porous media. The method can also be used for other types of problems, such as determining the stress in a shaft under load. or the temperature distribution during steady state heat flow. In this discussion only calculations concerned with the flow of fluids in porous media will be considered. The method was introduced by R. V. Southwell in 1935.' THEORY The treatment given here follows that given by Enimons.2 Consider a porous medium to be replaced entirely by a net of tubes of equal length and uniform cross-sectional area as shown in part in Fig. 1. Assume that the net of tubes behaves exactly like the porous medium which it replaces; that is, the net can be made fine enough to reproduce exactly the porous medium. Assume also that Darcy's Law can be used to calculate the flow from one point to another point through these tubes. The flow from point 1 to point 0 is KA . ------ P-P) .......(11 where a is the distance between points: K is the "permeability" of a tube; A is the cross-sectional area of a tube; is the viscosity of the liquid in the porous medium; and (P1 — P0) is the pressure difference between point 1 and point 0. In like manner the flow can be calculated from points 2, 3, and 4 to point 0. The net flow into point 0 is Qo = KA/µa (P1 + P2 + P33 + P4-4P0) . . (2) MB For an incompressible fluid the net flow into point 0 will be zero or, Q. = 0. This says that at point 0 fluid is neither being accumulated nor depleted. 'Therefore. P1 + P2 + P3 + P4 - 4P0 = 0 .... (3) . If. now. with specified boundary conditions. the pressure i.; known at a finite number of points in a given region, as at the points shown in Fig. 1, Equation (3) will be satisfied at every point. If, on the other hand, the pressure is not known, the pressure can be guessed at these points. Then. unless the guess is perfect. Equation (3) will not be satisfied at all of the points. When Equatiol~ (3,) is not satisfietl. let d = P1 + I?, + P, + P, - If' .,....(4) where 6 is an apparent error and is called the residual at point 0. Equation (4) shows how much the pressure guess is in error at point 0 with respect to the surrounding points. A positive residual means that the pressure is too low, and a negative residual means that the pressure is too high. To bring the residual, 6. to zero in order to satisfy Equation (3). it is necessary to make changes in the pressure guesses. Equation (4) shows that a +1 change in Po will change the residual at point 0 by -4. A +1 change in the pressure at any of the four surrounding points will change the residual at point 0 by +l. Thus it can be seen that a change at any point will affect the residual at that point and the four surrounding points. By changing the pressure from point to point, all of the residuals can eventually be brought nearly to zero and the problem will be solved. This procedure is the essence of relaxation methods and is used to relax the residuals so that Equation (3) is satisfied at every point. The procedure can be most easily explained in detail by solving a simple problem. as Southwell says, "To explain every detail of a practical technique is to risk an appearance of complexity and difficulty which may repel the reader. A

Jan 1, 1951

By R. L. Parsons, Herman Dykstra

A numerical method for solving partial differential equations in steady state fluid flow is described. This method, known as the "relaxation method," has two advantages over analytical methods: (1) practically any problem can be solved, and (2) a solution can be obtained quickly. A disadvautage is that the solution is not general. The method is applied to core analysis and relative permeability measurement to calculate constriction effects and to calculate the true pressure drop measured by a center tap in a Hassler type relative permeability apparatus. Further applications are suggested. INTRODUCTION Many problems in fluid flow cannot be solved analytically because of the nature of the boundary conditions. For many problems, however. an exact answer is not necessary because boundary conditions are not exactly defined or the parameters describing the porous medium are not accurately known. The relaxation method can be used to obtain an approximate answer easily and quickly for the flow of incompressible fluids in porous media. The method can also be used for other types of problems, such as determining the stress in a shaft under load. or the temperature distribution during steady state heat flow. In this discussion only calculations concerned with the flow of fluids in porous media will be considered. The method was introduced by R. V. Southwell in 1935.' THEORY The treatment given here follows that given by Enimons.2 Consider a porous medium to be replaced entirely by a net of tubes of equal length and uniform cross-sectional area as shown in part in Fig. 1. Assume that the net of tubes behaves exactly like the porous medium which it replaces; that is, the net can be made fine enough to reproduce exactly the porous medium. Assume also that Darcy's Law can be used to calculate the flow from one point to another point through these tubes. The flow from point 1 to point 0 is KA . ------ P-P) .......(11 where a is the distance between points: K is the "permeability" of a tube; A is the cross-sectional area of a tube; is the viscosity of the liquid in the porous medium; and (P1 — P0) is the pressure difference between point 1 and point 0. In like manner the flow can be calculated from points 2, 3, and 4 to point 0. The net flow into point 0 is Qo = KA/µa (P1 + P2 + P33 + P4-4P0) . . (2) MB For an incompressible fluid the net flow into point 0 will be zero or, Q. = 0. This says that at point 0 fluid is neither being accumulated nor depleted. 'Therefore. P1 + P2 + P3 + P4 - 4P0 = 0 .... (3) . If. now. with specified boundary conditions. the pressure i.; known at a finite number of points in a given region, as at the points shown in Fig. 1, Equation (3) will be satisfied at every point. If, on the other hand, the pressure is not known, the pressure can be guessed at these points. Then. unless the guess is perfect. Equation (3) will not be satisfied at all of the points. When Equatiol~ (3,) is not satisfietl. let d = P1 + I?, + P, + P, - If' .,....(4) where 6 is an apparent error and is called the residual at point 0. Equation (4) shows how much the pressure guess is in error at point 0 with respect to the surrounding points. A positive residual means that the pressure is too low, and a negative residual means that the pressure is too high. To bring the residual, 6. to zero in order to satisfy Equation (3). it is necessary to make changes in the pressure guesses. Equation (4) shows that a +1 change in Po will change the residual at point 0 by -4. A +1 change in the pressure at any of the four surrounding points will change the residual at point 0 by +l. Thus it can be seen that a change at any point will affect the residual at that point and the four surrounding points. By changing the pressure from point to point, all of the residuals can eventually be brought nearly to zero and the problem will be solved. This procedure is the essence of relaxation methods and is used to relax the residuals so that Equation (3) is satisfied at every point. The procedure can be most easily explained in detail by solving a simple problem. as Southwell says, "To explain every detail of a practical technique is to risk an appearance of complexity and difficulty which may repel the reader. A

Jan 1, 1951

By J. O. Brittain, E. P. Lautenschlager, D. A. Kiewit

Compression tests were run in the temperature range of 700° to 900°C ox 0' phase NiAl intermetal-lic alloys of several grain sizes. At these temperatures the minimum strengths were observed at the stoichiometric composition. While significant increases in strength occurved in both the low-nickel (vacancy) and high-nickel (substitutional) regions, the highest strengths were found in the high-nickel region. During deformation serrated flow was sometimes observed in the low-nickel alloys. After deformation transgranular cvacking and deformation striations were observed in all compositions tested. AS part of a general investigation of the properties of NiAl inter metallic compounds, a preliminary study of the role of point defects upon plasticity was made by high-temperature compression tests on ß' NiAl specimens of several grain sizes and compositions. ß' NiAl is an intermetallic compound having a CsCl structure and a rather wide range of composition from A1-45 at. pct to 60 at. pct Ni.1 According to Bradley and Taylor2 and to cooper,' it possesses a defect lattice in which departures from stoichiometry in the direction of decreased nickel content lead to the presence of vacant nickel sites (although Cooper's work indicates that a small amount of substitution also occurs) whereas departures on the high-nickel side lead to substitution of nickel on aluminum sites. NiAl forms congru-ently from the melt at approximately 1650°C,1 and thus has a higher melting point than either of its component elements. Up to this time, although this and other high-melting intermetallic compounds have been suggested for elevated-temperature usage,4 only the hardness4 and a few tensile-strength measurements5 have been reported for NiAl at high temperatures. In the present investigation the effects of composition upon the compressive-strength properties in a range of 700° to 900°C have been measured for NiAl of several grain sizes. EXPERIMENTAL PROCEDURES The alloys were made as described elsewhere6 from an A1-46.8 at. pct Ni master alloy furnished by the International Nickel Co. with additions of high-purity nickel and aluminum. The charges were vacuum-induction-melted in A12O3 crucibles with small amounts of helium added to the atmosphere to suppress vaporization. They were cooled slowly from the melting temperature to achieve uniform grain size. In order to refine the as-grown grain size a special rolling technique was developed. Alloys were packed into 0.10-in. wall-type 302 stainless-steel tubes which were partially filled with magnesium oxide to prevent bonding between the alloy and the steel jacket. The ends of the tubes were closed by hot forging, and the packets were then hot-rolled. The alloys with greater than 50 at. pct Ni were rolled at 1100°C, but it was found necessary to increase the temperature to 1350° C before alloys with less than 50 at. pct Ni would roll without cracking. With these temperatures, reductions as high as 48 pct were achieved in a single pass. The rolled alloys will hereafter be referred to as "fine grained" whereas the as-grown material will be designated "coarse-grained''. The compression specimens were made by cutting square cross-sectional pieces, approximately 3/16 by 3/16 by 1/2 in., with a water-cooled diamond cut-off wheel from the as-grown or the rolled alloys. Specimens were ground to their final dimensions by polishing through 3/0 grit silicon carbide papers. The final shape was a rectangular parallelepiped of square cross section having a height-to-width ratio of 3:1. Compression testing was carried out in a compression rig of our own design mounted on an In-stron Floor Model. The specimen chamber could be heated to 1000°C and was controlled within ±2°C. The compression rig was enclosed within a bell jar and was maintained at a 50 µ of mercury vacuum throughout the duration of the test. The test cham -ber was heated from room to test temperature within 15 min. Specimens were then held at the test temperature 30 min prior to testing. Previous experiments indicated that no grain growth would occur within this time. An Instron Variable Crosshead speed unit was used to adjust for small variations in specimen lengths in order to have a constant initial strain rate, €, for all specimens of a group. For the fine-grained specimens the strain rate was changed rapidly at constant temperature by a factor of 10 with the speed lever on the Instron. For a given € the compression data was analyzed in terms of true plastic strain (E) and true compressive stress (0).

Jan 1, 1965

R. Schuhmann, Jr. (Purdue University)— Fulton and Chipman's results on rate of silica reduction from slags are analogous in many was to the results of Parlee, Seagle, and Schuhmann10 on rate of alumina reduction from alumina crucibles. Both investigations have given comparably low rates of reduction and slow approaches to equilibrium. Accordingly, we may hypothesize that the rate-determining step is the same in both kinds of experiments; that is, oxygen diffusion across the stagnant boundary layer on the liquid-metal side of the interface between the liquid metal and the oxide phase (slag or solid oxide). I suggest that silica reduction involves the following consecutive steps: I) At the slag-metal interface: SiO2(slag) Si+ 20 II) Transport of oxygen from slag-metal to gas-metal interface: a) diffusion across liquid-metal boundary layer at slag-metal interface. b) convection within the body of liquid metal. c) diffusion across boundary layer at metal-gas interface. 111) At the metal-gas interface: C +O- CO (gas) Iv) At the graphite-metal interface: C (graphite) -C At steelmaking temperatures it is reasonable to assume that equilibrium is attained in all three chemical reactions (I, 111, and IV) right at the respective interfaces. Convection within the stirred liquid metal (step IIb) is also rapid. Transport of Si and C should be orders of magnitude easier than transport of 0, because of the relatively high concentrations of Si and C. Accordingly, we might expect the overall reaction rate to be determined by boundary-layer diffusion of oxygen, either IIa or IIc. Fulton and Chipman's demonstration that bubbling CO through the system had no major effect on reaction rate indicates that IIc is not the slowest step. Therefore, it becomes logical to estimate the maximum rate for step IIa and to compare this theoretical estimate with Fulton and Chipman's experimental data. If oxygen diffusion across the liquid metal boundary layer at the slag metal interface (step IIa) is rate-determining, In this equation, dn sio, /dt is the rate of silica reduction in moles per sec,A is the area of slag-metal interface in sq cm, Do is the diffusivity of oxygen in sq cm per sec, 6, is the boundary layer thickness in cm, c,* is the oxygen concentration right at the slag-metal interface in moles per cubic cm, and co is the oxygen concentration in the body of the liquid metal, also in moles per cubic cm. Equilibrium data" on the silicon deoxidation reaction in liquid iron and steel at 1600°C indicate that the oxygen contents of the liquid metal in Fulton and Chipman's experiments at 1600°C probably fell in the range of 0.5 x10-3 x10-3wt pct. That is, the maximum conceivable value of co*-co for the system under consideration was on the order of 10"5 mole oxygen per cubic cm. On the basis of previously published data,1O,11 it is estimated that Do/0 will fall somewhere in the range from 10-3 to 10-1 cm per sec. The surface area A in Fulton and Chipman's experiments was approximately 20 sq cm, and the weight of metal involved was about 500 grams. Combination of all these figures with the above rate equation leads to an estimate that the rate of silica reduction should fall within the range from 0.002 to 0.2 wt pct Si per hr. This estimate is consistent with the experimental data. For example, Fulton and Chipman's Fig. 2 shows a change of about 0.3 pct Si in 10 hr, corresponding to an average rate of 0.03 pct per hr. According to the proposed hypothesis, increasing the temperature will increase the reaction rate ill two ways: 1) by increasing oxygen diffusivity and 2) by increasing the oxygen concentration (oxygen solubility) in the liquid metal. The combination of these two effects accounts for the high value of the observed activation energy. Summarizing, I propose that the rate of silica reduction, like that of the carbon-oxygen reaction, is diffusion controlled and that low oxygen concentration in the liquid metal is the major factor accounting for the very low observed rates of silica reduction. John Chipman (author's reply)—The authors thank Professor Schuhmann for his interesting contribution. His proposed explanation may well prove to be the correct one. There is clearly a need for much further experimental work on this problem, and further research is in progress.

Jan 1, 1961

By T. L. Chu, G. A. Gruber

Silica films hare been rleposited 011 silicon substmtes at 400° to 600°C by a chemical-transport technique using hydrogen fluoride as the transport agent ill a closed system. This transport takes place from a source materia1 1071: temperature to substrates at higher temperatures, as indicated by the thermochemistry of the transport reaction. The experimental variables of- the transport process, such as the substrate temperature, the pressure pi the transport agent, and so forth, have been studied. The rate -determining step of the transport process appears to he the ),ale of chemical reaction in the source region. The transported films are similar to thermally grown silica films in physical proper-ties with the exception of 'some what higher dissolrrtion rates. SILICA films deposited on suitable substrates serve many purposes in electronic devices. They are used for the fabrication of tunneling devices, the surface passivation of devices, and the shielding of devices from nuclear radiation: and as selective masks against the diffusion of specific impurities into semiconductors. Doped silica films can also be used as sources for the diffusion of impurities into semiconductors. Several oxidation and deposition techniques for the preparation of silica films have been developed to meet the requirements of these applications. The therma1 oxidation of silicon by oxygen or steam at temperatures above 900 C is commonly used in silicon technology. The deposition techniques are perhaps more advantageous since they usually require lower temperatures and are not limited to silicon substrates. Silica films have been deposited on silicon and other substrates by reactive sputtering and chemical reactions. The sputtering of silicon in an oxygen atmosphere is capable of depositing good-quality silica films on silicon' and gallium arenide. Many chemical reactions are known to yield silica at room temperature or higher. These reactions may involve intermediate steps. However, the final step yielding silica should take place predominately on the substrate surface in order to produce adherent films. When silica is formed in the gas phase by volume reactions, no adherent deposit can be obtained. Generally, the experimental conditions of a reaction can be varied so that the surface reaction predominates over the volume reaction. The chemical reactions which have been used successfully for the deposition of silica films are briefly as follows. The pyrolysis of alkoxysilanes in an inert atmosphere or under reduced pressure has been employed to deposit silica films on germanium3 and silicon4 at 650" to 750°C in a flow system. The deposition of silica films from alkoxysilanes has also been achieved at nearly room temperature by a low-pressure plasma. Device quality silica films have been deposited on germanium and gallium arsenide by the deposition of an amorphous thin silicon film followed by oxidation at 600" to 700" . Silica films for high-temperature capacitors have been produced by the hydrolysis of silicon tetrabromide at 950°C in argon and hydrogen atmospheres.7 We have developed a chemical-transport technique for the deposition of silica films on semiconductor substrates at relatively low temperatures. The thermochemistry of the transport reaction, the experimental variables of the transport process, and the properties of the transported silica films are described in this paper. THERMOCHEMICAL CONSDERATIONS The transport of solid substances by chemical reactions in the presence of a temperature gradient has been used for the preparation of films and crystals of many electronic materials. In this technique, a gaseous reagent is chosen so that it reacts reversibly with the solid substance under consideration to form volatile products. Since the equilibrium constants of most reactions are temperature-dependent, the transport of these products to regions of suitable temperature in the reaction system would cause the reverse reaction to take place. depositing the original solid. When the equilibrium is shifted toward the formation of the solid as the temperature is decreased, the solid is transported from a high-temperature zone to a lower-temperature region, and vice versa. This chemical-transport technique can be carried out in a closed or gas-flow system. In a closed system, chemical equilibrium is presumably established in the different temperature regions of the system, and the transport agent regenerated in the deposition region repeats the transport process in a cyclic manner. The local chemical equilibrium may not be approached in a flow system: however, this system offers a greater degree of flexibility. Silica reacts reversibly with hydrogen fluoride and this reaction was chosen for the transport process. The over-all reaction between silica and hydrogen fluoride may be written as: SiO2(s) + 4HF(g-) = SiF4Ur) + 2H2O(^)

Jan 1, 1965

By E. C. W. Perryman

The wide grooves formed at the grain boundaries when high purity aluminum is attacked by hydrochloric acid or sodium hydroxide have been attributed by earlier workers to the high energy of the grain boundary material. The effect has been investigated for high-purity AI-Fe alloys with up to 0.055 pct Fe as a function of iron content and heat treatment. It is shown that the explanation given above is untenable, but that the results can be explained on the assumption that iron segregates to the grain boundary in solid solution. IN 1934, Rohrmann¹ showed that aluminum of 99.95 pct purity suffered intercrystalline corrosion when immersed in 10 to 20 pct hydrochloric acid, and that the susceptibility to intercrystalline corrosion depended upon the heat treatment given. The greatest susceptibility was found for specimens quenched from a high temperature (600°C) and the lowest susceptibility for specimens cooled slowly from that temperature. Lacombe and Yannaquis2 have shown that super-pure aluminum (99.9986 pct) annealed at 600°C suffers intercrystalline attack in 10 pct hydrochloric acid and that this attack is intensified by anodic dissolution in the same solution at a current density of 10 milliamperes per sq dm. No difference in extent of intercrystalline attack was found between the 99.993 and 99.986 pct Al, which led the authors to suggest that impurities played only a secondary role in the mechanism of intercrystalline corrosion. It was found, however, that the attack at the grain boundaries depended upon the relative orientation of the grains, large differences in orientation favoring rapid attack. Boundaries where the two neighboring grains were similarly orientated showed high resistance to attack as did boundaries between grains which were in twin relationship. These observations led Lacombe and Yannaquis to suggest that the intercrystalline attack was due to lattice discontinuities present at grain boundaries. Assuming that the grain boundary is a layer three to five atoms thick and has a crystal structure which is a compromise between the two neighboring grains it is clear that the discontinuities will increase with increasing difference in orientation between the neighboring grains and hence the increasing tendency to intercrystalline attack. Roald and Streicher³ investigated the effect of heat treatment of aluminum alloys ranging in purity from 99.2 to 99.998 pct on the corrosion resistance in 20 pct hydrochloric acid and 0.30N sodium hydroxide. They found that in hydrochloric acid the intercrystalline attack appeared to be determined by the type and quantity of impurities present and by the relative orientation of the grains. No difference in the susceptibility to intercrystalline attack was observed between specimens quenched and those furnace cooled, from 575°C. In 0.30N sodium hydroxide some materials exhibited intercrystalline attack, this taking the form of V-notches. Rohrmann¹ offered no explanation for the greater susceptibility to corrosion of material quenched from 600°C. It seems possible that this difference is connected in some way with a different distribution of impurity elements in the quenched and slowly cooled specimens. The fact that Roald and Streicher8 observed no difference between quenched and slowly cooled specimens may possibly be due to differences in either rate of cooling or silicon content or possibly both. Both these would be expected to have an effect on the distribution of impurity elements. Although the rate of cooling used by Rohrmann was slightly more rapid than that used by Roald and Streicher the position cannot be clarified because Rohrmann does not give the silicon content and Roald and Streicher give the silicon contents of only a few of their alloys. That Lacombe and Yannaquis2 found no difference in corrosion behavior attributable to impurities between the two materials they used may be because both were of high purity compared with the aluminum used by Rohrmann.¹ Although they found no difference in the corrosion behavior of their two materials it is possible that the results obtained by Lacombe and Yannaquis may, nevertheless, have been influenced by impurity distribution, since, on the transition lattice theory of grain boundary structure, it would be expected that sparingly soluble impurities would tend to segregate to boundaries where the orientation difference is such that there is a greater density of atomic sites of suitable size to contain them. It was considered worth while, therefore, to examine the corrosion properties of a series of materials of differing impurity content with the objects of confirming the experimental observations made

Jan 1, 1954

By D. A. Kraai, S. Floreen

The effect of 1 to 50 ppm S on the ductility of nickel at 800° to 1400°F was studied. Results at each temperature showed a decrease in the reduction of area from approximately 95 to 5 pet over the sulfur range studied. Ductility varied with grain size, but only to a minor extent relative to the sulfiw effect. The effects of sulfur were completely offset by the addition of small amounts of magnesium. The results indicate that the "hot-short" loss in ductility is not an inherent property of nickel. Some possible mechanisms which cause the loss in ductility are described. MANY metals or alloys that normally possess high ductility exhibit a ductility loss at intermediate temperatures. This loss in ductility is often called "hot-shortness". Numerous examples of this phenomenon have been reported in the literature. Much of this work has been reviewed by McLean1 and by Rhines and Wray.2 To date there is no fully satisfactory explanation of the cause of this intermediate-temperature hot-shortness. It is generally recognized that impurities, and particularly impurities that form low-melting phases, can cause embrittlement. Examples of hot-shortness have been reported, however, where there were no obvious impurities present which would lower the ductility. Thus there has been some basis for believing that hot-shortness is an inherent property, and that even the purest metal would display a hot-short loss in ductility. This latter hypothesis was recently put forward by Rhines and wray2 based on studies of nickel and nickel alloys. In the discussion of this paper, however, Guard noted that high-purity nickel showed no hot-shortness.3 Thus there is reason to doubt whether pure nickel, or by inference any other pure metal, will inherently exhibit hot-shortness. The present work was initiated to determine the extent to which hot ductility was sensitive to very small amounts of an impurity element. If it could be demonstrated that hot-shortness could be induced by only minor amounts of an impurity, then it might be argued that hot-shortness in general is an impurity effect, and not a fundamental property of pure metals. The particular impurity studied was sulfur in nickel. The deleterious effects of sulfur are well- known. It is also well-known, and will be shown below, that additions of magnesium will render sulfur innocuous. When no such refining agents are added, however, the Ni-S system is a very useful one for studying the influence of small amounts of impurities. EXPERIMENTAL PROCEDURE Two heats containing -24 ppm S were vacuum-melted and small amounts of magnesium were then added under an argon atmosphere. These alloys were used to show the effectiveness of the normal magnesium treatment in overcoming the influence of sulfur. A second series of alloys with a sulfur range of 1 to 50 ppm was then prepared by vacuum melting nickel in alumina crucibles. No elements, such as magnesium, which tend to combine with sulfur were added. The higher sulfur contents were attained by adding nickel sulfide. Lower sulfur contents were prepared using a method in which the melt was oxidized under vacuum to produce the reaction S + 2O = SO2 These heats were subsequently deoxidized with carbon. Ten- to twenty-pound ingots were cast of all of the alloys studied. The compositions are given in Table I. The ingots were forged and hot-rolled to 3/4-in. bar. They were then annealed at either 2000" or 1600°F to produce different grain sizes. One-quarter-in.-diam tensile specimens were machined from the bars. These were tested at 800°, 1000o, 1200°, and 1400°F. The specimens were held at temperature approximately 45 min before testing. The strain rates were 0.005 min-1 to yielding, and 0.05 min-' after yielding. No extensometers or gage marks were placed on the specimens because the higher sulfur heats tended to fracture at the knife-edge indentations or gage marks. The properties measured were ultimate tensile strength and reduction of area. The analytical technique for determining sulfur at low levels was that developed by Burke and Davis.4 They reported a standard deviation of 1 ppm at an average sulfur level of 4 ppm in NBS standards. A standard deviation of 3 ppm is probably more realistic for the alloys used in this investigation considering the possibility of some segregation in the ingots. RESULTS A summary of the tensile results is given in Table I. As shown in the table, both heats to which

Jan 1, 1964

By Bruce Chalmers, D. C. Larson

Aluminum crystals with longitudinal-axis orientations of (111) . (110), and (100) were deforined in tension and annealed. The conditions of deformation were controlled so that the re crystallization nuclei originated in either the heavily deformed regions at saw cuts {artificial nucleation) or in the lightly deformed matrix (spontaneous nucleation). The artificial-nucleatioln experiments showed that in lightly deformed (110) and (100) crystals low-angle twist boundaries are most mobile, while in (111> crystals and heavily deformed (110) and (100) crystals high-angle tilt boundaries with near (111) rotations are favored. The spontaneous-nucleation experiments showed the existence of preferred orientations in the (111) crystals. The nonrandomness of the grain orientations is quantitatively determined through a comparison with the results which would he obtained from a randowl set of grain ovientations. PREVIOUS recrystallization studies have been performed on single crystals deformed in tension.1 7 The crystals used in these studies usually had random tensile-axis orientations and the extent of deformation was not a primary consideration. The present study concerns the recrystallization of single crystals with tensile-axis orientations of (Ill), (110), and (100). The emphasis of this work is on the influence of the tensile-axis orientation and the degree of deformation on both the nucleation and growth processes. The multiple-slip orientations were chosen because secondary slip or slip intersection promotes nucleation.1,5,8 These crystals recrystallize at lower strains than the crystals which are oriented for single slip. Also, the greatest variation in deformation behavior is exhibited by the multiple-slip orientations. The stress-strain curves for crystals with tensile-axis orientations of (111) are higher than the stress-strain curves for poly-crystals, and the stress-strain curves for crystals with tensile-axis orientations of (100) are lower (at large strains) than the stress-strain curves for the crystals which deform initially in single slip.g The recrystallization nuclei originated in either 1) the homogeneously* deformed matrix of the crys- tals or 2) the heavily and inhomogeneously deformed regions at saw cuts. The nuclei will be referred to hereafter as spontaneous and artificial nuclei, respectively. The two terms do not imply a difference in the nature of the nuclei; they imply simply a difference in the mode of introduction of the nuclei. During spontaneous nucleation very few (always less than ten) grains nucleate, while during artificial nucleation large numbers of grains nucleate. Only a fraction of the artificially nucleated grains penetrate very far into the deformed matrix during annealing. The grains that penetrate the farthest into the deformed matrix will be referred to as the dominant grains. EXPERIMENTAL PROCEDURE The thirty-five crystals used in this investigation were grown from the melt in milled graphite boats at a rate of 1.6 cm per hr. The crystals had dimensions of approximately 6 by 12 by 80 or 6 by 6 by 80 mm and the aluminum was of 99.992 pet purity. The as-grown crystals were annealed at 610°C for 24 hr and furnace-cooled. They were then heavily etched and electropolished in a solution of five parts methanol to one part perchloric acid. The crystal orientations were obtained by back-reflection Laue photographs and were accurate to ±2 deg. The tensile-axis orientations were (loo), (110), and (111). Two of the side faces of the (111) crystals were (110) lanes. The (110) crystals had both {100) and {110) side faces and the (100) crystals had (100) side faces. The crystals were deformed at a strain rate of 0.003 per min. Shear stress and shear strain were obtained by multiplying and dividing the tensile stress and strain, respectively, by the Schmid factor, m. For the (111) crystals m = 0.272 and for the (110) and the (100) crystals m = 0.408. The Schmid factor is effectively constant during deformation for all orientations. The deformed crystals were sawed into 1-in.-long specimens while the crystals were totally enclosed in a graphite boat. The sawing was performed very carefully in order to limit the plastic deformation to the sawed regions. The specimens were electropolished in the solution mentioned above to remove the sawed-end deformation as well as controlled amounts of surface material. A special stainless-steel grip was used to hold the specimens during the electropolishing treatment. The gripping faces were flat, with no teeth, to prevent the introduction of extraneous de-

Jan 1, 1964

By H. C. Gatos, A. D. Kurtz

WITH the growing interest in the mechanism of self-diffusion of metals, the study of accurate and convenient methods for determining self-diffu-sion coefficients appears highly desirable. It was with this objective in mind that the present investigation was undertaken. Gatos and Azzam1 employed an autoradiographic technique for measuring self-diffusion coefficients of gold. This method involved sectioning of the specimen through the diffusion zone and recording the radioactivity directly on a photographic film. Because of the very short range of the emitted ß rays in gold, the activity recorded on the film was essentially the true surface activity. With proper choice of the sectioning angle, sufficient resolution could be obtained and the entire concentration-distance curve recorded in one measurement. For the boundary conditions of the experiment, where an infinitesimally thin layer of radioactive material diffuses in positive and negative directions into the end faces of a rod of infinite length, the solution of the diffusion equation is C/Cn = 1/v4pDt exp (-x2/4Dt) where C is the concentration of diffusing element (photographic density in this case), C,, is the constant (depending upon amount of radioactive material), x is the diffusion distance, D is the diffusion coefficient, and t is the time. Thus, by plotting the logarithm of the concentration vs the square of the diffusion distance, a straight line results and the slope contains the diffusion coefficient. In this manner, the self-diffusion coefficient of gold can be obtained as a function of temperature. In the present investigation the results reported by Gatos and Azzam1 have been verified, and the autoradiographic technique has been further developed and applied for the determination of the self-diffusion coefficient of gold at a number of temperatures. Furthermore, the energy of activation for the self-diffusion of gold has been conveniently determined. . Experimental Techniques Preparation of Specimens: The inert gold of high purity was received in the form of a rod from which cylinders were cut and machined to a diameter of 0.500 in. The specimens were annealed to a suitably large grain size and the faces were surface ground prior to the deposition of the radioactive layer. The radioactive isotope Au198 was chosen. It was produced in the Brookhaven pile by means of the reaction Au197 + n ? Au108. It decays by ß emission (0.96 mev) to Hg108 with the subsequent emission of a y ray (0.41 mev). 70Au 108 ? 80Hg 108 + -1e°. The half life of the Au108 is 2.7 days so that a strict time schedule had to be maintained in order to secure sufficient activity until the end of the experiments. For this reason, initial activities as high as 10,000 millicuries per gram were used. The gold arrived in the form of foil and was evaporated onto one face of each gold specimen cylinder to a thickness of about 100A. A sandwich-type specimen was formed by welding two such cylinders together. Evaporation of Gold: The gold was evaporated under vacuum from heated tantalum strips which were bent in such a way as to limit the solid angle through which the gold was allowed to vaporize, thus insuring a more efficient utilization of the gold. The specimens rested on flat brass rings which had an inner diameter of 0.475 in. The entire specimen-holding assembly could be manipulated from outside the vacuum system by means of a magnet which attracted a slug of soft iron attached to the assembly. By evaporating inert gold on glass slides under conditions identical to those employed for the radioactive gold, it was found that the thickness of the films was about 100A. Welding: The welding was performed by hot pressing in a stainless steel cylinder. The inside of the cylinder was threaded and fitted for two plugs. The specimens to be welded were placed in the middle of the cylinder and two pressing disks, one at each end, were inserted to avoid shearing stresses as the plugs were tightened. Mica disks were placed between the pressing disks and the specimens to prevent them from welding. The plugs were then tightened with a hand wrench and the entire unit was placed in an argon stream for about an hour to remove the oxygen. The unit was then inserted in the center of an argon atmosphere furnace maintained at about 700°C and left there for about an hour. Because of the difference in the temperature coefficient of expansion of the two metals, as the temperature rose. the pressure on the specimen-rollple increased and a weld resulted Welding was generally satisfactory under the conditions described.

Jan 1, 1955

By Sandford S. Cole, John S. Breitenstein

The recovery of over 80 pct of the vanadium values in titaniferous magnetite from Maclntyre Development,Tahawus, N. Y., was accomplished by an oxidizing roast with Na2O3-NaCI addition. Process description is given for leaching of roasted ore and precipitation of V2O5 and Cr2O8 from leach liquor. THE exploration and development of the Mac-Intyre orebody at Tahawus, N. Y., by the National Lead Co. provided a source of vanadium. Analyses of various composite sections of the drill cores of the MacIntyre orebody were made to establish whether or not the vanadium was constant throughout. Ten drill cores were sampled as 50 ft sections, crushed, and a portion magnetically concentrated. The head and concentrate were analyzed for total iron and vanadium. The results on the concentrates indicated that the vanadium is associated with the magnetite and maintains a close ratio to the iron content. The nominal ratio of 1:25:140 of V: TiO2:Fe was found to exist in the concentrates. Typical value for the vanadium in the magnetite both from laboratory concentration and mill production is 0.4 pct. The recovery of vanadium from the magnetite was investigated in 1942 to 1943. The research program encompassed both laboratory and pilot-plant work on sufficient scale to provide adequate data to establish the feasibility of a full scale plant. The recovery of vanadium from various ores has been reported in the literature and has been the subject of many patents. The literature dealing with recovery from titaniferous ore by roasting is quite limited. Roasting with alkaline sodium chloride, sodium chloride or alkaline earth chlorides, and sodium acid sulphate have been claimed in various processes as effective means.1-8 The reduction of the ore, followed by acid leaching, was another method proposed.'-' "he use of various pyrometallurgical processes for recovery of vanadium in the metal or in the slag has also been extensively investigated, but the results had little application to the problem."-" The separation of vanadium values from subsequent leach liquors and vanadium-bearing solution has been the subject of a considerable number of papers and patents. The most practical is by hydrolysis at a pH of 2 to 3 by acidifying a slightly alkaline solution. Data on solubility of V²O5 and V2O4 in water and in dilute sulphuric acid indicated a solubility of 10 g per liter in water.'" Laboratory Results Magnetite Analysis: Adequate stock of magnetite was provided so that the laboratory and pilot-plant operation was on ore representative of the mill production. The ore was analyzed chemically and examined by petrographic methods to ascertain whether the vanadium was present in combined state or as an interstitial component between grain boundaries. No evidence was obtained which would indicate that the vanadium was in a free state as coulsonite.15 The analysis of the ore was as follows: Fe²O³, 47.4 pct; FeO, 29.1; TiO,, 10.1; V, 0.40; and Cr, 0.2. The screen analysis of the ore on the as-received basis was: -20 +30 mesh, 28.8 pct; —30 +40, 18.9; -40 +50, 9.7; -50 +60, 15.1; -60 4-100, 5.9; -100 + 200, 11.2; -200 +325, 3.7; and -325, 7.2. Roasting Conditions: The prior practice indicated that a chloridizing roast with or without an alkaline salt had been effective on other titaniferous magnetites. On this basis roasts with additions of sodium chloride, sodium carbonate and mixtures thereof were investigated varying the roasting temperature between 800" and 1100°C. Since the ore had shown no segregation or concentration of vanadium, the influence of particle size on the freeing of vanadium by the reagents during roasting was determined. The initial work was on silica trays in an electric resistance furnace with occasional rabbling of the charge. Subsequently, the roasting was carried out in a small Herreshoff furnace to establish the influence of products of combustion on the recovery of the vanadium. The laboratory tests showed that this ore required an alkaline chloridizing roast, in conjunction with a reduction in particle size to less than 200 mesh. When roasted in air at 900 °C with 5 pct NaCl and 10 pct Na2CO³, over 80 pct recovery of the vanadium was attained as a water-soluble salt. The presence of alkaline earth elements gave detrimental effects and care had to be exercised to avoid any contamination of the ore or roast product by such materials. The solubilization of vanadium under the various conditions is given in a series of curves in Figs. 1 to

Jan 1, 1952

By W. Rostoker, R. F. Domagala, R. P. Elliott

The phase equilibria of the Hg-Th system over the composition range 0-100 pct Th and temperatures up to 1000°C have been studied for a small-volume, closed system. The solubility of Th in liquid Hg is about 5 pct at 300°C and decreases sharply with decreasing temperature. Two intermediate phases occur, Hg3 Th and HgTh. The structures of these are hexagonal (nonideally close-packed) and face-centered cubic, respectively. The HgTh phase decomposes eutectoidally at 400°-500°C. The solubility of Hg in solid thorium seems to be negligible. AFULL-phase diagram for this system would have to be defined on temperature-composition-pressure co-ordinates. This paper describes the pseudo phase diagram of a closed system, that is, where the alloy enclosed in a small volume equilibrates with a vapor pressure of mercury dictated by composition and temperature. Because of the experimental difficulties in studying a system of this nature, many of the phase relations can only be sketched. Alloy Preparation Alloys over the full range of composition were made from triple distilled mercury and one of two grades of thorium. For the bulk of the work, a calcium-reduced metal in sintered pellet form of reported 99+ pct total thorium content was used. Arc-melted specimens of this thorium gave a hardness of 135 VPN. The microstructure showed small primary dendrites of ThO2. A number of alloy compositions were made with a high-purity, iodide-decomposition thorium metal. The are-melted hardness of a button of this material was 35 VPN. Although the microstructure of the arc-melted specimens showed no dendrites of ThO2, there was definite evidence of an unidentified phase enveloping the grain bound-aries. There were no distinguishable differences between the constitution of alloys made with the two grades of thorium metal. Under normal conditions thorium is not wetted by liquid mercury. The film of ThO2 on all thorium metal cannot be penetrated by either liquid or vaporous mercury. It was therefore necessary to comminute thorium in the presence of mercury under such conditions that oxide films could not reform on the newly exposed metal surfaces. This was accomplished by the use of a high-speed, carbide-tipped rotary cutter incorporated in a chamber purged with argon and connected at the bottom to a demountable Vycor bulb containing a weighed amount of mercury. This experimental device is fully described in a separate paper.1 Alloy compositions were calculated by weighing the empty bulb, the bulb containing the mercury, and the bulb containing the mercury and the thorium chips. Many alloys were analyzed chemically for thorium and/or mercury after subsequent homogenization; the agreement between analyzed and calculated compositions was invariably very close. Bulbs containing the requisite amounts of mercury and fine thorium chips were clamped off, removed to a sealing unit, evacuated and sealed. Amalgamation under these conditions proceeded rapidly even at room temperature. To insure homogeneity, the specimens were annealed to 300-400°C. Alloys containing less than 30 pct Th remained pasty after all treatments, indicating an equilibrium condition of liquid plus solid. Alloys with more than 30 pct Th were transformed into a dark powdery product. These latter specimens were annealed for times of up to 1 week to complete interdiffusion. Many of the alloy compositions are pyrophoric. On exposure to air they oxidize with considerable evolution of heat to a mixture of ThO2 and free mercury. It was mandatory that alloy specimens be handled in a "dry box" purged thoroughly with argon. All X-ray diffraction specimens were powdered, screened, and sealed in capillary tubes within the dry box. Experimental Procedures Thermal analysis experiments, useful only in the mercury-rich region of the system, were conducted with the alloys in their original containers. A reentrant thermocouple well formed an integral part of the bulb. These bulbs were heated in a silicone oil bath and cooled in a dry ice-acetone mixture. The rates of heating and cooling were slowed by immersing the specimen bulb in a larger tube containing silicone oil. This provided a suitable thermal lag. In all tests, pure mercury was run as a basic standard. While the invariant reaction at about the melting point of mercury was detected by thermal analysis, the heat effect at the liquidus was not sufficient to produce an inflection in the cooling curve. It was necessary to determine the liquidus temperatures at the mercury-rich end of the system by "breaks" in electrical reslstivity versus temperature curves for individual alloys. The apparatus for this purpose consisted of a pyrex tube about 2 in. diam and 12 in

Jan 1, 1959

By John C. Sawyer

The mechanism of catastrophic oxidation of chromium and 446 stainless steel is examined. Data are presented to show that accelerated oxidation of these two materials, as caused by lead oxide, can occur in the absence of a liquid layer contrary to presently accepted theory. An alternate theory is proposed in which the rate of accelerated oxidation is a function of the rate at which lead oxide destroys the protective oxide formed on the base metal. An example of the application of the theory is given for the catastrophic oxidation of chromium in the presence of lead oxide. WHEN stainless iron-, nickel-, or cobalt-base alloys are heated in air to moderate temperatures in the presence of certain metallic oxides, oxidation will proceed at an accelerated rate. This phenomenon, often called "catastrophic oxidation", is most pronounced for the stainless steels. With these alloys the condition is so severe that large masses of oxide will form on the surface of the alloy in 1 hr or less at temperatures of 1200o to 1700oF. While a number of oxides are known to cause this effect, PbO, V2O5, and Moo3 are the most familiar, having been the subject of one or more investigations which have appeared in the literature.1-7 In presenting the results of these investigations, many of the authors have offered possible explanations to account for the more rapid rate of oxidation observed; however, the liquid layer theory as proposed by Rathenau and Meijering 2 has been the most commonly accepted mechanism. The liquid layer theory proposes that a low-melting oxide layer is formed on the surface of the alloy as the result of the interaction of the alloy oxide and the contaminating oxide. When the temperature of oxidation is above the melting point of the oxide on the surface, a liquid layer will form and oxidation will proceed at an accelerated rate. At temperatures below the melting point of the surface oxide, oxidation will proceed more slowly in the normal manner. It is argued that the rates of diffusion of oxygen and metal ions through the liquid layer are extremely rapid thereby accounting for the high rate of oxidation. Various experimental data have been presented to show that the temperature at which accelerated oxidation first becomes apparent coincides with the melting point of the eutectic oxide which would be present on the surface. Some exceptions have been observed, e.g., silver will oxidize in the presence of Moo3 at temperatures below the lowest melting eutectic; on the other hand, stainless steel will not be catastrophically oxidized at 1500oF in a molten bath of PbO and SiO2. In reviewing the various theories which have been used to explain catastrophic oxidation, Kubaschewski and Hopkins 8 favor the liquid layer theory, but note that, ".. .as experimental observations are not altogether in agreement with this theory (liquid layer theory), one should consider it a necessary but not a sufficient condition." In contemplating the liquid layer theory, it appears that sufficient evidence has not been presented to establish the theory beyond question. As a means of further clarification, a program of research was undertaken to determine in greater detail the mechanism of accelerated oxidation as caused by lead oxide. The first part of the program deals with a comparison of the oxidation of both AISI 446 stainless steel and chromium metal in the presence of lead oxide, vs the oxidation of these two materials in air alone. These comparisons are made at a number of different temperatures, most of which are below the melting point of the surface oxides. The second part of the program is concerned with a presentation of an alternate theory of accelerated oxidation exemplified by the system Cr-PbO-Air. PROCEDURE AND RESULTS Several experimental methods are commonly used to follow the progress of oxidation. One of these, the weight-gain method, was chosen for this work. This procedure requires that a specimen of the alloy be weighed, oxidized for a given period of time at an elevated temperature, and reweighed—the difference between the two weights being noted. The weight gain of the specimen represents the amount of oxygen acquired from the atmosphere to transform a portion of the specimen to oxide. In those cases where there is a tendency for the specimen or oxide to volatilize at the testing temperature, additional data must be collected so that a correction factor can be determined. This factor must be applied to the weight change in order to ascertain the actual amount of oxidation which has taken place. The specimens used for this work were 1 1/2 in.

Jan 1, 1963