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By R. L. Frink

I FEAR that my treatment of this subject may not, in all instances, meet the approval of those who read my opinion as to the utility and efficiency of pyrometers in the making of glass, or bottle-glass. It may be superfluous for me to add that this opening statement is based on over 15 years' experience in an endeavor to successfully apply pyrometers, or heat-measuring instruments, to glass-melting furnaces, particularly the type known as tank-furnaces, and that such endeavors have proved more or less futile. It is my desire, therefore, to herein set forth the problems encountered, hoping thereby to stimulate further effort in the successful application of pyrometers. It is my desire, also, to invite criticism of the methods used and suggestions from those who may have a wider experience, or who may have better methods. Fin. 1.-GLASS TANK FURNACE. In general, I believe that the inefficient application of pyrometry to the melting of glass in tank furnaces is not due as much to the instruments as to the conditions under which they must be used and the character of the medium in which they must reside. Most of those present no doubt, are familiar, at least in a general way, with the methods and apparatus used in the melting and making of bottle-glass, or glass that is formed into containers of various shapes and designs. Most of this glass is made in what is known as a tank furnace, these furnaces vary widely in design and construction. In general, they consist of a rectangular tank-like form, built up of fireclay blocks, and range from 2 by 4 ft. (0.6 by 1.2 m.) to 24 by 140 ft. (7.3 by 42.6 m.) with a depth of glass from 2 to 5 ft.; or a capacity of from approximately. 2 to 700 tons. Fig. 1 shows the general

Jan 9, 1919

By A. H. Bell

The general principles of the gas-lift will not be described in this paper. Only specific details that have not been fully discussed in previous papers, or results that do not fully coincide with conditions previously described, will be dealt with. The principal points to be emphasized and for which supporting data are furnished are as follows: 1. Gas-lift installations usually have comparatively high efficiencies as compared with standard pumping equipment, when reduced to a basis of barrels produced per horsepower installed. 2. Advantages of high-pressure plants from the standpoint of operating efficiency and for the application of the gas-lift early in the life of flowing wells. 3. Evidence of increased ultimate yield through conservation of gas by the gas-lift. 4. Possibility of development of new equipment to increase efficiency of the gas-lift. 5. Indications of the advantages of repressuring as a means of stabilizing gas-lift wells and as a means of increasing ultimate yields. TyPes of Installation The gas-lift installations of the more important companies in California have been of the central-plant type wherever field conditions would permit. This has resulted in greater flexibility and lower installation costs per well than could be obtained with individual well units. In general discussions of the gas-lift method of production, the installation costs are frequently referred to as being too high for economical operation. If the field conditions are carefully analyzed and the plant designed with the idea of obtaining high operating efficiencies, the installation cost per well can be lowered sufficiently to compare favorably with individual well-pumping units, when the operating advantages are considered. Much greater production per horsepower can be obtained with the gas-lift than is possible with pumping equipment. Table 1 shows the unit sizes and costs of gas-lift installations of three companies in the Los Angeles basin. The cost of walking beams, rods,

Jan 1, 1928

By Leland Van Wert

IN 1888, Howard,1 working at the Watertown Arsenal on the tensile properties of ferrous materials at various temperatures, noted the curious fact that the stress-strain diagrams of low-carbon steels tested within a certain temperature range (200° to 350° C.) departed more or less from the normal regularity of such diagrams as secured by testing at either above or below these temperatures. This same jagged appearance of similar diagrams for steels has been observed by at least one other investigator, and de Forest2 has reported similar irregularities in the tensile testing of some nonferrous alloys. Recently again, this anomaly in diagram contour has been shown in a most striking fashion, apparently because of its accentuation by the method of testing employed, by Dr. Albert Sauveur.3 He described (for nonaustenitic steels) two quite distinct types of torsional stress-time diagrams: (1) those with a regular and smooth outline, derived normally by testing at temperatures above 300° C., or below 200° C. (as, for example, Figs. 4a or e); and (2) those presenting a decided "stepped" appearance, which are invariably produced when twisting is done within the 200° to 300° C. range (examples, Figs. 5a and b). The torsion test brings out so much more sharply (and convincingly) the irregularities occurring at 200° and 300° C. than does the tensile test that they can no longer be considered as resulting from simply idiosyncratic or accidental and inconsequential causes. Clearly, from the temperatures involved, the "stepped" type of diagram, or more accurately, the peculiar manner of response to torsional stress which manifests itself in the diagram, is an aspect of the "blue-heat" phenomenon. One's curiosity if, nothing else, prompts an inquiry as to the nature and significance of these "steps." What do they mean? What causes them? To these questions there are no completely satisfactory answers. The following experimental observations are offered as suggestions towards the solution of the problem.

Jan 1, 1931

Illinois is rightly known as containing the coal deposit of which the first record in the United States was made. Joliet and Marquette saw "charbon de terre" along the Illinois River in 1673;1 LaSalle saw "mines de charbon" along the same stream in 1679; and Hennepin reported having "found in Several Places Some Pit-Coal" in 1682.2 In 1687 Jontel, in writing of the Illinois River country said, "along the river are coal pits, the coal whereof has been try'd and found very good."3 J. Carver reported the northern parts of the Mississippi River valley, "containing lead, copper, iron, coals, etc." in 17664 evidently referring to the Illinois country. Croghan, in the same year, saw coal along the Wabash River, near the mouth of the Vermilion in Indiana, but not far from Danville. Capt. Philip Pittman in his journey up the Mississippi in 1770 reported that "great pieces of coal are constantly found on the sand-banks, from whence it may be concluded, that there are coal-mines on the upper parts of the Mississipppi."5 This coal could only have come from the Illinois or Big Muddy Rivers. Morse, in 1798, refers to great quantities of coal on the upper branches of "the Father of Waters," and "on the Illinois River is a coal mine, which extends for half a mile along the middle of its banks."6 While, undoubtedly, some coal was used locally in various places, no records have been left of it and the first definite one is that in 1809 William Boon shipped some coal from the Big Muddy River, in Jackson County, to New Orleans, which was the first coal exported from Illinois.1 There has been considerable discussion as to this first shipment, whether it was made in 1809, 1810 or 1812. The records of arrivals of: boats in New Orleans in those early years is specific as to date, name of craft and name of captain, but no mention is made of cargo carried. William Boon arrived

Jan 1, 1942

By W. B. Gogarty, W. C. Tosch

A new recovery process for producing oil under both secondary and tertiary conditions utilizes the unique properties of micellar solutions (also known as microemulsions, swollen micelles, and soluble oils). These solutions, which displace 100 percent of the oil in the reservoir contacted, can be driven through the reservoir with water and are stable in the presence of reservoir water and rock. Basic components of micellar solutions are surfactant, hydrocarbon and water. They may also contain small amounts of electrolytes and co surfactants such as a1cohol.r. The specific reservoir application dictates the type and concentration of each component. A salient feature of [he process is the capability for mobility control. Micellar solution slug mobility, by way of viscosity control, is made equal to or less than the combined oil and water mobility. Mobility control continues with a mobility buffer that prevents drive water from contacting the micellar solution. Laboratory and field flooding have proven that the process is technically feasible and that surfactant losses by adsorption on porous media are small. Introduction projects are under way to recover the maximum amount of oil under the most favorable economic conditions.' : New techniques are being developed to increase oil recovery,3" Polymer solutions are becoming an important means of controlling mobility in a waterflood. Thermal methods such as in-situ combustion and steam injection are being used in reservoirs containing highly viscous crudes. Surfactant flooding is receiving attention as a method of reducing interfacial tension to increase recovery.*'" Exotic recovery processes have been considered primarily for ' perations. Economics are unfavorable in most cases for tertiary recovery. studies at the Denver Research Center of the Marathon oil CO. have led to a new oil recovery method.* Micellar solutions (sometimes called microemulsions, swollen micelles, and soluble oils) are used to recover oil by miscible-type waterflooding. Basically, these solutions contain surfactant, hydrocarbon, and water. The method can be used in either secondary or tertiary operations. First, thc concept of thc process is considered in terms of the requirements for an effective miscible waterflood ing operation. Next, micellar solution properties are described including structure, composition, and phase behavior with reservoir fluids. Fluid characteristics are then considered as related to mobility control, and, finally, laboratory and field results are presented to illustrate the efficiency of the process. Concept of the Process Unit displacement efficiency and conformance determine the effectiveness of any oil recovery mechanism. In theory, a miscible waterflood should be capable of a 100-percent unit displacement efficiency with a correspondingly high conformance. Requirements for the slug of a miscible waterflood include (1) 100-percent displacement of oil in the reservoir contacted, (2) controllable mobility, (3) the capability of being driven through the reservoir with water, (4) a low unit cost to enhance economics, and (5) the ability to remain stable in the presence of reservoir water and rock. Micellar solutions satisfy requirements for the slug of a miscible waterflood process. Our discovery that these solutions acted as though they were miscible by displacing all fluids in the reservoir and by being displaced by water solved the miscibility problem. Adequate mobility control is possible by variations in solution viscosity through compositional changes. Economic requirements are met since micellar solution costs below $6/bbl appear possible, Mi cellar solutions stabilize surfactant in the presence of reservoir rock and water, thus reducing the importance of the problem of surfactant loss by adsorption. Fig. 1 illustrates schematically how these solutions are used. Operations start with injection of a micellar solution slug that serves as the oil displacing agent. Next, a mobility buffer of either a water-external emulsion or water solution containing polymer (thickened water) is injected to protect the slug from water invasion. Finally, drive water (water used in a regular waterflood) is injected to propel the slug and mobility buffer through the reservoir. Reservoir oil and water are displaced ahead of the slug, and a stabilized oil and water bank develops as shown in Fig. 1. Stabilized bank saturations are independent of original oil and water saturations. This means that, for a particular type of reservoir, the displacement mechanism is the same under secondary and tertiary recovery conditions. Oil is produced first in a secondary operation. For tertiary conditions, water is produced first. Movement of the slug through the reservoir is stabilized by the mobility buffer. An unfavorable mobility ratio usually exists at the interface between the buffer and drive

Jan 1, 1969

By H. W. Mossman

Three aspects of magnetite smelting are discussed. The first is the working out of equilibrium conditions for eliminating sulfur. The second is the influence of magnetite solubility on the difficulty of tapping the reverb matte. The third is an approximation of the equilibrium conditions in the reverb gases which govern whether magnetite is mode or reduced in the reverb slag by these gases and by any iron sulfide in the slag. MAGNETITE has had a varied history in the Hurley Smelter since its start in 1939. Magnetite determinations on the smelter products are made regularly only on the monthly composite samples. Variations on the monthly averages are shown in Table I. Magnetite which drops from the slag and matte in the reverb has some slight bottom buildup which comes and goes, but no substantial accumulation from this source has been found at the end of a normal nine months' furnace campaign. However, there has been some low grade magnetite bearing material mixed with considerable A1,0,, which has slid down from the bottom of the sloping flue between the reverberatory furnace and the waste heat boilers. This accretion has required drilling and blasting near the skimming end of the furnace. The magnetite has interfered with tapping at times. When the smelter was first started, tapping trouble from magnetite was extremely severe. Increasing the reverberatory furnace temperature by putting in an air preheater and a Dutch oven has helped greatly, although there still is occasional tapping trouble. When the present series of physical chemistry articles on copper smelting started coming out in 1950, they were read with interest, but no immediate application was seen for them. Results of some laboratory work in 1952 aroused a much stronger interest in this physical chemistry. A series of melts was made on some converter slags, which had magnetite in very large grain sizes, with the object of reducing the grain sizes in the slag, as it was known that it was easier to handle in the reverb in that condition. Anything done in the tests greatly reduced the grain sizes—even in the controls, where nothing was done except melt the slag and cast it. There was more magnetite in the slags after the tests than before, and with wide variations. There were no obvious reasons lor much of what happened in these tests. Much of the base material published in English in this field was made available for study. Recalculations were made on many of the type problems, and part of the data was reduced to local temperatures and compositions. Explanations were found for what happened in the 1952 series of tests on converter slags, and the same principles turned out to be a description of much of what magnetite does in the reverb. This article is to present the results of that study, from the viewpoint of applying the technical material in definite numerical form to the operating conditions in both the converters and the reverberatory furnaces at the Hurley smelter. Table I. Magnetite Variations on Monthly Averages, 1939 to 1955 Pet Magnetite Lowest Highest Average Converter slag 13.6 43.3 25.4 Roverb slaa 2.7 20.9 8.7 Matte 28 15.9 98 In general it was found that magnetite is made or reduced in both the converters and the rever-beratory furnace, depending on variations of temperature, matte composition, and reverb gas composition occurring in ordinary plant operation. Within reasonable limits, the field conditions for formation or reduction can be predicted, and probably can be set up and maintained. Converter conditions affecting magnetite formation can be put into numerical values better than for the reverb from purely technical calculations. The converter can be operated so as to keep the magnetite in the slag down to between 12 and 14 pct and still give satisfactory life for the converter brick. This depends upon having converter flux available which will make a slag with a good separation without raising the temperature too high. In the Hurley reverb and others with similar conditions, it is likely that a compromise of conditions will give a reasonably good control of combustion and still keep the magnetite from building up on the bottom. This discussion consists of three main parts. The first is the working out of the equilibrium conditions in the converter for determining in which direction the reaction 3 Fe,,O, (s) + FeS (1) F? 10 FeO (1) + SO, will go under actual converter operating conditions. The second deals with the influence of the solubility of magnetite in the slag and matte in the reverb on the difficulty of tapping matte. The third is an approximation of the equilibrium conditions in the

Jan 1, 1957

By C. F. Allen, G. B. Walker

The sink-float methods designated by heavy-media separation processes were pioneered by C. Erb Weunsch for the treatment of base metal ores as an improvement over jigs. The work of Weunsch was further developed by Victor Rakowsky and The American Zinc, Lead and Smelting Co. Early in the development of the processes, the inherent unsuitability of galena as the solid constituent of the medium was recognized and ferrous media amenable to magnetic recovery and control were developed. The high efficiency and low cost of magnetic recovery and cleaning of ferrous media regardless of particle size, slime contamination, or surfacial oxidation had led to the adoption of ferrous media by all of the sink-float plants operating under the heavy-media separation processes patents controlled by American Zinc, Lead and Smelting Co. Approximately 2,000,000 tons of base metal and nonmetallic minerals are treated each month by these methods. Heavy-media separation processes are a modern practical and economical adaptation of the well-known laboratory procedure for separating a mixture of two solids by immersing the mixture in a liquid having a specific gravity intermediate the specific gravities of two solids. The lighter solid floats while the heavier sinks. This method of separation has been attempted on a commercial scale, but the high loss and high cost of the organic liquids halted the development of the process. Many attempts have been made to simulate a heavy liquid by using a suspension of a finely divided solid in water. If the solid phase of the suspension is ground fine enough, the suspension can be made stable or so slow settling that a substantially uniform specific gravity can be maintained from top to bottom of the bath. However, any material separated by such methods will inevitably be contaminated by some slime which will eventually accumulate in the bath and cause a viscous medium at the expense of separating efficiency. Therefore, it is necessary to provide means for continually cleaning a portion of the medium to eliminate slime at the same rate at which it is introduced to the medium. The problem of efficiently cleaning the medium limits the minimum grain size of the solid of the suspension in the case of the Chance sand process for cleaning coal, because de-cantation is the only cleaning method available. If the sand is too fine, it will be lost along with the slime. Therefore, coarse sand must be used, and to maintain a semblance of a uniform suspension, it is necessary to use strong rising water currents. The combination results in a separation based more on hindered settling classification than on sink-float principles. As previously mentioned, galena was used as the solid constituent of the medium during the early stages of the development work. The high specific gravity of galena made it suitable for the preparation of medium for high specific gravity separations. Galena can be cleaned by either decantation or by froth flotation. As with sand, de-cantation limits the minimum particle size of the media that can be cleaned without excessive loss. Froth flotation for cleaning galena medium has been used, but the problem of floating fine galena that has been exposed to extensive oxidation is well known to be a most difficult one. Last year the largest heavy-media plant m the world, and the second plant to be installed, converted from galena medium to ferrous medium despite the fact that the ore contains galena which can be used as medium. The change to ferrous medium has been beneficial in many ways. Today all the heavy-media plants have been converted from galena to ferrous media. Unquestionably, ferrous media have the widest application of any media developed, for the following reasons: 1. Ease of recovery and cleaning by magnetic means. Particle size or surface condition not a factor. 2. Low consumption per ton of ore treated. 3. Resistance to abrasion. 4. Widest range of media densities, including higher workable densities (1.25 to 3.4) than have been found possible with nonferrous media. 5. Space required for recovery and cleaning of ferrous media is considerably less than that for nonferrous media. 6. Ferrous media require lower capital investment and operating costs for media recovery and cleaning. Advantages of Heavy-media Separation Processes Heavy-media separation processes offer the following positive advantages, amply demonstrated on a wide variety

Jan 1, 1950

By Charles L. Mantell, George Ferment

This investigation determined the jeasibility of current-potential curves as an analytical tool for monitoving manganese electroicinning solutions for metallic impurities. Nine metallic impurities were studied: trickel, cobalt, silver, copper, zinc, molybdenum, catlmiun magnesium, and sodium. The individual effect of each metallic irzplrl,iLy on the standard point-izatiorr was determined for a range of 'concentration. Not all of Ihe impurities affected the polarization curve; correlation between transition current and cotrcetztration of impurity. Molybdenum had an uncorrelated effect on the polarization curie. The effects of binary mixtures of impurities were studied to see if the transition current of the mixture could be predicted. Interactions occurred between impurities which prei'etzted the pvecliction the transition current of tile rrlisLitr.e by additive laws. The polarization curve was shown to be sensitive to metallic impurities which affect the current efficiency of a manganese cell. THE application of current-potential curves in manganese electrowinning is not new but played an important part in the conversion of an inoperative large-scale pilot plant into a continuous comnercial operation.1"" The effects of trace metallic impurities in manganese electrowinning solutions on cathode current-potential curves,5-19 specifically nine impurities (nickel, cobalt, silver, copper, zinc, molybdenum, cadmium, magnesium, and sodium) were studied for a range of concentrations. Cadmium, magnesium, and sodium had no effect. Nickel, cobalt, silver, copper, and zinc yielded a correlation between transition current and concentration of impurity: molybdenum had an uncorrelated effect. Binary mixtures of impurities were studied to de-termine if the transition current could be predicted from the values for the individual constituents. Interactions between impurities prevented the prediction of the transition current of the mixtures by an additive law. The polarization curve was shown to be sensitive to metallic impurities which affected the rurrent efficiency of a manganese cell. The electrowinning of manganese relies upon maintaining a high-purity electrolyte. Purification schemes were developed to remove all of the heavy metals, the magnesium and calcium. Concentration limits have been established for single impurities. With high-purity electrolytes, favorable cell efficiencies are consistently obtained; but with impure solutions there is a reduction in efficiency. With the rapid rise to commercial prominence of electrochemical processes, there has been a lag in developing rapid methods for determining whether an electrolyte is sufficiently pure for efficient electrolysis. The most sensitive test for impurities is the behavior of the electrochemical cell. Impure electrolytes will cause a serious reduction in cell efficiency, and in many cases metal deposition will be prevented or reversed. The effects of impurities are not usually evident until after long periods of electrolysis, resulting in a disruption of the process. A method which could predict the behavior of an electrolyte in terms of cell efficiency prior to reaching the commercial cell is needed. Van Arsdale and Maier," Allmand and Campbell,a1'22 and others attempted to develop an electrochemical process for manganese,"3"29 but all met with some degree of difficulty. Jacobs et a studied the effects of metallic impurities in manganese electrowinning. Plant methods were based on a 2-hr plating in a small electrolytic cell. The final method was based on a 24-hr plating run, performed in a relatively large test cell. Here, current efficiencies were calculated with and without impurities in the electrolyte, and the critical concentration was established as the maximum amount of impurity that the electrolyte could tolerate before there was a serious loss in efficiency. The amount of impurity that could be tolerated decreased as the plating time increased, indicating deposition of the impurity. This test duplicated the conditions of commercial practire, and was sensitive to impurities. Small amounts of impurities significantly affect the hydrogen overvoltage at a metal surface, increasing or decreasing it depending upon the nature of the impurity. ockris established the limit for the onset of poisoning at 10-l moles per liter. The effects of impurities were studied by potential-time curves at a constant current density. The technique did not lend itself to rapid analysis in that several hours were needed to establish stable potential-time curves. Serfass and coworkers3' developed calorimetric and spectrophotometric techniques for analyzing for trace impurities. Our method4'" is based on current-cathode potential curves produced by continuously changing the cell voltage at a programmed rate. Starting with a clean stainless-steel cathode, the cell voltage was initially adjusted to yield zero current: the program was then started and the current was plotted as a function of the cathode potential. Fig. 1 is a typical current-potential curve. In initial region A the hydrogen-evolution reaction predominates and the polarization curve

Jan 1, 1967

By C. M. Loeb, A. M. Gaudin, J. H. Brown

THE object of most size reduction operations in the mineral industry is to liberate the grains of valuable minerals in the ore from those of the gangue. This is usually accomplished by crushing and grinding the entire mass of ore until there is only a small probability that any single particle contains more than one mineral. During this size reduction only limited control exists over size or composition of the particles exposed to the breaking action, and there is no control over the paths followed by cracks generated during the operation. This lack of control usually results in overgrinding and in production of large quantities of very fine material. The first detriment, overgrinding, is costly in itself, but when combined with the second factor it is doubly so. Not only is the fracture of a free particle unnecessary—the fracture of these particles may also make subsequent separation operations difficult, inefficient, and wasteful. It has been pointed out' that if the object of size reduction is to liberate the valuable mineral component of the ore then, ideally, fracture should follow intergranular paths to the exclusion of trans-granular ones. This would result in liberation of the valuable minerals with as little size reduction as possible. This ideal comminution operation is referred to as intergranular comminution, and it was the object of the investigation to determine the extent to which it could be developed by heat treatments. There are many indications in the literature that heating rocks prior to crushing may be favorable. Reports by Holman,2 Yates3 and Myers' are pertinent. These investigators showed that heating certain rocks prior to crushing them did, in fact, improve their crushing characteristics in that fewer fines were produced, although the fact that intergranular comminution was being effected apparently was overlooked. In addition, Sosman noted that if there is appreciable anisotropism in the thermal coefficients of expansion of even a pure mineral, then considerable permanent separation of the grains of the rock can be expected as a result of heating the rock to a high temperature.' By the same token, if there are ap- preciable differences in the thermal expansion coefficients of the various minerals of a multi-component rock, similar results should be obtained by heating this rock. This has been tested, partially, by Brenner," who obtained patents covering the heat treatment of some pegmatitic rocks in order to facilitate comminution of these materials. It has also been demonstrated that this may occur in taconite." Also, the possibility of causing decomposition of one mineral in a rock as a means of promoting intergranular fracture has been considered. Seigle2 and Schiffman et al. have obtained patents on such processes as applied to calcareous iron ores. These reports all indicate that heat treatments prior to crushing may contribute materially to intergranular comminution, but they also indicate that no organized attempt has been made to determine the controlling factors of the method or to determine its applicability in general. The present article is a report on the initial phase of such an investigation. The authors have reviewed the claims of prior investigators and have attempted, also, to establish the factors that might determine the applicability of heat treatments in the mineral industry. In this work 2000-g samples of various rocks were heated in a small laboratory furnace and crushing and sizing operations were carried out in standard laboratory equipment. All samples of each rock were as nearly identical as possible in particle size, grain size, and composition and contained only lumps coarse enough to contain many grains each. Tests on Granite A number of tests were made on a coarse grained Finnish granite obtained in the form of coarse chips from a local monument yard. This rock exhibited little variation from piece to piece in either composition or grain size. The minerals contained were quartz, orthoclase, small amounts of hornblende, and minute quantities of mica. Grain size ranged from about 1 mm to about 3 mm. Temperature of the Heat Treatment: In some cases the granite was heated to a particular temperature and crushed, hot, immediately upon withdrawal from the furnace—in others the rock was allowed to cool before crushing, but without quenching to room temperature after heating. In most tests on granite the heating period was about 2 hr with the furnace at the highest temperature for about 1 hr. Cases in which these periods were varied greatly will be presented separately.

Jan 1, 1959

By Neils Hansen

The microstructure of dispersion-strengthened aluminum aluminum-oxide products containing from 0.2 to 4.7 wt pct of aluminum oxide has been examined by optical and transmission electron microscopy, and the flow stress has been determined at room temperature and at 400C by tensile testing. Products were examined as recrystallized and as high-temperature extruded, and the microstructures consisted of a fine dispersion of oxide particles in a matrix divided by respectively recrystallized grain boundaries and subgrain boundaries. The flow stress (0.2 pct offset) at room temperature of recrystallized dispersion strengthened aluminum aluminum-oxide products is the superposition of dispersion strengthening and grain boundary strengthening. This superposition has been found to be linear. The flow stress (a) can be related to the grain size (t) by the Petch equation: ing content of oxide and k is a constant independent of the oxide content. For extruded products a similar relation has been found by replacing the grain size by the subgrain size. The k-value is of the same order for the two types of structure, which shows that the subgrain boundaries are as effective slip barriers as grain boundaries. Tensile testing at 400C of re-crystallized and extruded products shows that oxide dispersion strengthening is very effective, whereas the strengthening effect of grain boundaries and subgrain boundaries is small. THE microstructure of dispersion-strengthened products consists of hard particles finely distributed in a metal matrix. The strengthening effect of the dispersed phase has been fairly well established,1 and it has been found that the size and volume fractions of the dispersed particles are important structural parameters. However, in many dispersion-strengthened products which have been worked and heat-treated during manufacture the matrix is divided into well-defined grains or sub-grains, which may also have a strengthening effect. A model of the matrix strengthening in dispersed products worked during manufacture has been proposed,2 introducing the energy of the structure as a strengthening factor, especially at low temperatures. A difficulty in this model is, however, to relate this (stored) energy to the structural parameters directly observable as for instance grain size. The strengthening effect of the matrix grain size after recrystallization has been in- vestigated for nickel-thoria (TD-Nickel) products3 and for copper aluminum-oxide products. Conclusive results were, however, not obtained as the grain size of TD-nickel was constant. 5 to II , after recrystallization at temperatures from 700 to 1200°C and as the copper products containing 5 to 1 wt pct of aluminum oxide could not be recrystallized even after severe cold reduction and heat treatment at 1050C. For aluminum aluminum-oxide products containing from 1 to 5 wt pct of aluminum oxide it has been shown that the tensile strength at room temperature decreases when an extruded product is cold-worked and recrystallized. The matrix in the extruded products is divided into well-defined subgrains of micron size, and as the grain size of the recrystallized products is about two orders of magnitude higher, it is obvious that grain boundary strengthening occurs. Preliminary results8 have indicated that the flow stress containing no grain boundaries, A is a constant and t is the subgrain size. At elevated temperatures the effect of boundaries is more complex; it has been shown11 that recrystallized products having an oxide content of about 3 wt pct are more creep resistant than extruded material in the temperature range 400° to 600°C, whereas on application of a higher strain rate the tensile flow stress (0.2 pct offset) is higher in extruded than in recrystallized aluminum—5 wt pct aluminum oxide products at temperatures from room temperature to 427°C (800), Finally it has been shown12 that the Brinell hardness at 350°C of extruded products having about the same content of aluminum oxide increases with decreasing grain size, determined by X-ray line-width measurements. The present study was undertaken to obtain a quantitative relationship between the tensile strength and the grain size of aluminum aluminum-oxide products in the recrystallized as well as in the extruded state. The tensile testing was performed at room temperature and at 400uC. The grain size of the recrystallized products was varied by changing the degree of cold-work preceding the recrystallization heat treatment. In extruded products grain (or subgrain) size variations were obtained by high-temperature heat treatment after extrusion. EXPERIMENTAL a) Materials. Aluminum aluminum-oxide products have been manufactured by consolidation of aluminum powder covered with a layer of aluminum oxide formed during powder manufacturing. The products examined were manufactured from atomized powder containing

Jan 1, 1970

By F. H. Wilson, M. L. Kronberg

The low temperature recrystalliza-tion of very heavily rolled copper produces a fine grained structure with a high degree of preferred orientation. Additional heating to within a few hundred degrees of the melting point may induce an abrupt and pronounced increase in the grain size, with the resulting crystals having new orientations. This behavior at high temperatures is commonly termed "secondary recrystallization." Several investigations have dealt with the phenomenon arid have served to bare many features of the beha~ior.1-4 In general,observations have been made on the sizes and shapes of the grains, and data have been presented showing the existence of an induction period in isothermal experiments. Although it has been well established that the orientation before the change is statistically (100) 10011, the so-called "cubically aligned" texture, there is no such agreement on the orientation after the change. For example, Dahl and Pawlek1 describe it as being equivalent to an approximately 30" rotation about the [l00] axis of the ideal cubic texture which is parallel to the rolling direction, the resulting orientation being near (210)[001]; and Cook and Richards2 find an orientation of approximately (110)[L12]. Since the completion of most of the work to be reported in this paper, Rowles and Boas3 have published their ver] illuminating paper on "secondary recrystallization," in which they present convincing evidence for a third orientation and show that their esperiments give no evidence for either of the other two orientations. The orientation is described as equivalent to an approximately 30° rotation about a [ 111] pole of the ideal cubic orientation. The existence of a variety of reported orientations is not unique for copper, for a similar state of affairs exists for other systems that have been studied— aluminum, nickel, nickel-iron alloys, and others. It seems therefore that the existence of this variety does not necessarily constitute a contradiction, but rather indicates that different experimental conditions yield different results. The fundamental nature of the phenomenon has not been elucidated. However, it has been generally recognized that the large grains could be the end product of growth of a few select grains already existing in the sample in minor amounts—too small to allow detection—or that entirely new ones could be formed by a process of nu-cleation and growth. Existing experimental evidence does not distinguish between these two most apparent possibilities. Nevertheless, the former has been more generally favored largely because our current understanding of the state of an annealed metal has not made it seem reasonable to expect a nucleation event to occur at temperatures above those required for the primary recrystallization. Observations on the Preparation and Heating of Twin-bearing Cubically Aligned Copper The starting material used throughout. the investigation was a bar of OFHC copper, forged and annealed at 950°C. Visual inspection showed the grain size to be around 0.5 mm, and did not disclose any preferred orientation. A chemical analysis showed the following composition: Cu + Ag— 99.99 Pct S — 0.005 pct 0 — <0.005 pct For the preparation of cubically aligned copper, ¾ in. thick slabs were cut from the bar, heavily pickled in concentrated HNO3 and cold rolled to sheets about 0.012 in. thick. The reduction in thickness was approximately 98.5 pct. Standardized annealing techniques were followed. Samples to be heated were lightly dusted with alumina in order to prevent sticking and then sandwiched between 1/16 in. copper plates. The resulting sandwich was heavily wrapped with copper sheet, and then annealed in air. The protection was such that only very thin films of oxide were formed. That the associated light oxidation of the samples had no specific effect on the recrystallization behavior was shown by the similar results that could be obtained on annealing in highly purified and dried hydrogen. Two methods were used in bringing samples to temperature: (1) by placing the package directly in the furnace at temperature and (2) by placing the package in the furnace at room temperature, and then slowly increasing the temperature. The corresponding heating rates are illustrated in Fig 1, and will be referred to as "rapid" and "slow," respectively. Unless specified otherwise, all anneals will be of the former type. Metallographic examination was made on samples prepared by electrolytic polishing and etching as described in the Metals Handhook.* STRUCTURES FOUND BEFORE "SECONDARY RECRYSTALLIZATION" OCCURS Annealing the rolled material for 1 hr at 400°C produced a heavily twinned, cubically aligned structure, the grain size being of the order of 0.03

Jan 1, 1950

By C. D. Williams, C. E. Ells

The susceptibility of quenched and aged Zr-2.5 wt pct Nb alloy to embritt2ement during irradiation has been examined for a number of solution temperatures and aging times. Material quenched from temperatures approximately 40°C below the transus has high tensile ductility, and this ductility is insensitive to aging at 500°C or to irradiation. If, however, the material is quenched from temperatures above the transus it becomes highly susceptible to loss of ductility either from aging at 500 or from irradiation. Inter granular failure is characteristic of the materials having low ductility. The distribution of the equilibrium phase is found to control the susceptibility to embrittlement by restricting 6 grain growth during heat treatment and thus influencing crack propagation. IN zirconium, as in titanium, -stabilizing alloy additions are used to obtain high strengths via quench and age heat treatments, and the Zr-2.5 pct Nb alloy has been developed1 because of its strength advantage over the Zircaloys. Early in the development of the Zr-2.5 pct Nb alloy the problem of 13 embrittlement was appreciated, and for this reason the solution temperature was chosen below the p transus.&apos; In the course of irradiation studies on quenched and aged Zr-2.5 wt pct Nb alloy it was found&apos; that irradiation introduced an important aspect of p embrittlement, riz., material quenched from the phase and aged 24 hr at 500°C was severely embrittled by moderate doses of neutron irradiation. This effect had not been studied in titanium alloys. In titanium the metallurgical features leading to 0 ernbrittlement were found to be structures with: a) coarse a platelets at the grain bondaries, b) finely dispersed a uniformly distributed throughout the (0) matrix,6 c) Widmanstatten a-13 with more than 50 pct P, d) the presence of some metastable p transformation products,3 and e) large prior -phase grain size.5 Alternatively, the presence of a uniform distribution of coarse a was conducive to high ductility and a structure largely of equiaxed a was very dctile. The detailed mechanisms of the embrittlement have not been worked out for all of these conditions, although weakness at either a-matrix boundaries or prior p grain boundaries have been prominent in the eculation. It was proposed that acicular a might act as a mild notch, and low ductility has been associated with easy fracture along its boundary.&apos; There have been two opposing suggestions for the source of the high ductility associated with equiaxed a phase. JaffeeB proposed that this a would accept a large por- tion of the oxygen, thus increasing the ductility of the matrix, whereas after study of a Zr-Nb-Cu alloy Weinstein and oltz proposed that the a phase, softer than the martensitic matrix, acted to blunt cracks formed in the matrix. In the present work we have studied the effect of neutron irradiation on the ductility, particularly the P embrittlement, of the Zr-2.5 wt pct Nb alloy. By a variation of solution temperature and aging time a variety of metallurgical conditions have been examined, and a range of resultant ductilities obtained. The ductility has been related to the material microstructure and mode of fracture. EXPERIMENTAL The alloy used in the present work came from two separate ingots fabricated into rod of 3/8 or i in. diam, Table I. For both batches the P transus temperature was approximately 890° C. Most of the heat treatments were done directly on lengths of the j} in. diam rod, after which the tensile test specimens were machined. Quenching was achieved by dropping rods from a dynamic vacuum into water, the cooling rate estimated to be 2 100°C per sec. For aging the rods were encapsulated in evacuated silica tubes. Round tensile test specimens, with gage diam and length 0.160 and 1.0 in., respectively, were used throughout and pulled at room temperature or 300°C on Instron tensile machines, at a crosshead speed of 0.05 ipm. Specimens were irradiated in the NRX and NRU reactors, in facilities described in previous publications.&apos;0 The metallurgical conditions examined have been: All tensile test specimens were machined with axes in the axial direction of the swaged rod. Although the specimen had a degree of preferred crystallo-graphic orientation with basal plane normals both parallel with and perpendicular to the tensile axis, the material was comparatively isotropic." The techniques of thin foil examination in the electron micro-

Jan 1, 1970

By Francis R. Conley, John A. Sievert, John N. Dew

A brief review is presented of the past performance of a number of large, thin, highly permeable reservoirs with low dips in the Bolivar Coastal fields of Venezuela. The performance of these reservoirs indicates that the fluids are segregated vertically within the sand section by gravity. With this assumption, equations are developed which describe the performance under pressure maintenance operations. Methods of solving these equations and results of simple example calculations are presented. Example calculations indicate that under pressure maintenance conditions injected gas tends to {tow preferentially along the top of the sands and that encroaching water has a tendency to flow preferentially along the bottom. The expected performance of segregated fluids is discussed and compared with that of fluids which are uniformly distributed in any sand section. INTRODUCTION The field performance of a number of reservoirs described herein indicates that the fluids are segregated vertically within the sand section by the force of gravity. Thus, it was felt that any method used to predict the future performance of these reservoirs should consider the effects of segregation in the sand sections. A study of the available information on some of the reservoirs suggests that increased recoveries may be expected if the reservoir pressure is maintained by either crestal gas injection or flank water injection. To predict future performance of reservoirs under pressure maintenance operations, a method of analysis was needed which would account for segregation of fluids in the sand sections. Several methods of analysis have been developed to take into account the segregation of fluids in the reservoir as a whole1,3 To our knowledge no method considers segregation of the fluids within sand sections in the manner indicated by the past performance of several reservoirs in the Mara-caibo Basin. This paper outlines part of the work done in studying some of these reservoirs and contains a description of their performance characteristics. The analysis presented is restricted to pressure maintenance conditions, since space limitations prevent a full discus- sion of the development of the mathematical relations and the various methods of solving them. Only a sketch of the development of the mathematical relations is given. The various methods of solving these relations are pointed out, but the actual determination of solutions to various problems are omitted except for one example. It is felt that these results may aid in the study of reservoirs outside the Maracaibo Basin. Some concepts on which the present analysis is based are outlined by D. N. Dietz. However, the analysis presented herein includes several factors not considered by Dietz: (1) variations in permeability and in the cross section, (2) various shapes of the cross section, and (3) the production of fluids. Also, the mathematical development presented by Dietz differs considerably from our corresponding analysis. RESERVOIR CHARACTERISTICS The reservoirs under consideration, large and thin, with low dip and high permeability, are large to the extent that they contain from 0.5 to over four billion bbl of oil initially in place. The section thicknesses vary from 100 to 400 ft and the lengths from 10,000 to 40,000 ft. Thus, a length-wise cross section of the producing formation appears to be long and thin. The dip angles vary from 0 to 6 degrees and the average permeabilities vary from 0.5 to over three darcies. The reservoirs contain from 20 to 50 per cent shale inter-laminated with the productive sands. Most shale breaks within the major sands do not correlate from one well to the next, and correlation is often difficult, even between wells drilled from the same location. However, it is often possible to correlate the shale breaks between major sands for some distance. Herein we are concerned with the performance of reservoirs containing oil of gravities over 20" API. Past reservoir performance indicates good pressure communication and, in cases where pressure sinks have developed, large amounts of fluid migration have occurred. Few of the reservoirs have had initial gas caps, but also, few have been found to be highly under-saturated. Due to gravity segregation, secondary gas caps usually form before the pressure has been reduced more than 25 per cent of its initial value. The effect of gravity has not only been apparent on a reservoir-wide basis, but has also caused segregation of the reservoir fluids in productive sections. Proof of this is found from the results of selective well tests, workovers, and electric and various other types of logs. Evidence that

By R. G. Agarwal, Ramey Jr. H. J., Al-Hussainy R.

Although it has long been realized that gas recovery from a water-drive gas reservoir may be poor because of high residual saturations under water drive, it appears that only limited infomlation on the subject has been available until recently. This study was performed to show the qiiantitative potential importance of water influx. Results indicate that gas recovery may be very low in some cases: perhaps as low as 45 per cent of the initial gas in place. Gas recovery under water drive appear to depend in an important was on: (I) the prodirction rate and manner of production; (2) the residual gas saturation; (3) aquifer propertie.); and (4) the volumetric displacement effciency of water invading the gas reservoir. The manner of estimating water-drive gas reservoir recovery can vary considerably. Examples are: the steady-state tnethorl. the Hurst modified steady-state method, and various unsteady-state methods such ac. those of van Ever-dingen-Hurst, Hurst, and Carter-Tracy. The Carter-Tracy water influx expression was used in this study. In certain cases, it appears that gas recovery can be increased significantly by controlling the production rate and manner of production. For this reason, the potential importance of water influx in particular gas reservoirs should he investigated early to permit adequtrtr planning lo optirtize the pay reserves. INTRODUCTION In recent years, the economic importance of natural gas production has become increasingly apparent. This has been evidenced by more intensive exploration efforts aimed at gas production, and exploitation of both deep, as well as low-permeability gas reservoirs. Technical developments such as deep-penetration fracturing have made development of such formations economically feasible. Unfortunately, water influx has forced abandonment of a number of gas reservoirs at extraordinarily high pressures. Although reservoir engineering methods for estimating water influx have long been available, it appears that application of these methods to the water-drive gas reservoir has been sporadic.&apos;a Available methods for estimating water influx which can be applied to the water-drive gas reservoir problem include the steady-state method,1 the Hurst modified steady-state method and various unsteady-state methods such as those of van Everdingen-Hurst. Hurst, and Carter-Tracy. Interesting applications of these solu- tions to gas reservoir and the aquifer gas-storage problems have appeared recently.3,12,14 The experimental study of residual gas saturations under water drive by Geffen et al. in 1952 indicated that residual gas saturations could be extremely high. A value of 35 per cent of pore volume is often used in field practice when specific information is not available. The study of Geffen et al. showed that residual gas saturation might be much higher in some cases. Naar and Henderson concluded that the residual non-wetting phase saturation under imbibition should be about half of the initial non-wetting phase saturation. The Naar and Henderson result that residual gas saturation under water influx should be about half the original gas saturation is recommended as an estimate if laboratory measurements are not available. Thus, it is clear that a considerable portion of the initial gas in place might be trapped in a water-drive gas reservoir as residual gas at high pressure. A full water-drive would result in loss of residual gas trapped at initial reser.voir pressure. Consideration of transient aquifer behavior leads to the conclusion that high-rate production of water-drive gas reservoirs could result in improved gas recovery by reduction of the abandonment pressure. However, there appears to be little quantitative information on this possibility. One of the few advantages of water-drive gas production appears to be improved deliverability through water-drive support of the reservoir pressure. There may also be an advantage in higher condensate recovery caused by pressure maintenance for gas-condensate water-drive reservoirs. In view of the preceding, this study was made to assess the potential importance of water-drive in gas reservoir engineering. The Carter-Tracy approximate water-influx expression was used because this equation offers some advantages in hand-calculation which do not appear to have been generally recognized.&apos; However, calculations were performed in the main with a high-speed digital computer to permit evaluation of the effect of water-drive under a large variety of conditions. CALCULATION METHOD Water-drive gas reservoir performance can be estimated in a manner completely analogous to oil reservoir calculations: a materials balance is written for the reservoir, and a water influx equation is written for the aquifer. Siniltaneous solution provides the cun~ulative water influx and the reservoir pressure. When reservoir performance data (gas produced and reservoir pressures) are available, it is usually possible to match performance data to determine the initial gas in place and the water influx parameters —

Jan 1, 1966

By E. Miller, J. M. Eldridge, K. L. Komarek

The thermodynamic properties of liquid Mg-Ge alloys have been determined between 1000°and 1500°K by an isopiestic method. Germanium specimens, heated in a temperature gradient and contained in covered graphite crucibles of special geometry, were equilibrated with magrtesium vapor in closed titanium tubes. The crucible design allowed free access of magnesium vapor to the samples during the equilibration to form alloys of magnesium and germanium, but prevented magnesium losses from the crucibles on quenching the titaniuin tubes to terminate the experimental runs, thus preserving the equilibrium alloy compositions. The activities and partial molar enthalpies of magnesium and the integral thermodynamic properties of the system were calculated from the experimental data. THE Mg-Ge phase diagram&apos; shows one congruent melting compound, Mg2Ge, of essentially stoichio-metric composition, two eutectics, and very limited terminal solid solubilities. Very little information is available on the thermodynamic properties of the Mg-Ge system. The free energy of formation of Mg,Ge was recently deter-mined2 by a Knudsen cell technique in the temperature range 610° to 760°C. The standard enthalpy of formation of Mg,Ge was measured calorimetrically by Bever and coworkers.3 The present study was undertaken as part of a general investigation of the thermodynamic properties of the homologous series of Mg-Group IVB systems, i.e., Mg-Pb,4 Mg-Sn,5 Mg-Ge, and Mg-Si. An isopiestic technique was used which was developed by the authors5 for investigating the thermodynamic properties of liquid Mg-Sn alloys. Specimens of the nonvolatile component, contained in covered graphite crucibles, are heated in a temperature gradient in an evacuated and sealed titanium reaction tube, and equilibrated with magnesium vapor of known pressure. The method employs crucibles of special geometry which preserve the high-temperature equilibrium composition of liquid alloys having a highly volatile component such as magnesium on termination of the experimental runs by quenching the crucibles to room temperature. EXPERIMENTAL PROCEDURE First reduction germanium of 99.999+ pct purity (Eagle-Pitcher Co., Cincinnati, Ohio) and 99.99+ pct magnesium metal (Dominion Magnesium Ltd., Toronto, Canada) were used. The graphite crucibles were machined from high-density (1.92 g per cu cm) graphite rods (Basic Carbon Corp., Sanborn, N.Y.) which had a maximum ash content of less than 0.04 pct. The non-reactivity of graphite with germanium at the temperatures used in this study had been previously established by Scace and Sleck.6 The experimental procedure has been previously described in detail.5 The selection of a particular crucible geometry for a run was determined by a combination of imposed experimental conditions, the principle being that more tightly covered crucibles were required to preserve alloy compositions during quenching when higher magnesium pressures and higher specimen temperatures were used. Depending upon the composition range of the equilibrated alloys the source of the magnesium vapor was either pure magnesium or a two-phase mixture of Mg2Ge + Ge-rich liquid of known magnesium pressure. The experimental runs can be divided into the following three groups on the basis of crucible geometry and magnesium source material. Crucibles with Small Holes and Pure Magnesium Reservoirs. The crucible dimensions were identical to those of the Mg-Sn investigation5 except that the hole diameters were reduced to 0.010 in. because of the higher temperatures and higher magnesium pressures involved in the Mg-Ge system. During an equilibration run, magnesium vapor diffused from the reservoir to each specimen through the small holes, one drilled through the crucible lid and two others drilled through graphite baffles positioned vertically inside the crucible between the lid hole and the specimen. Since the magnesium pressure was high, i.e., in the range 117 to 277 Torr, during the equilibration time of approximately 24 hr, equilibration was not impeded by these holes. A specimen composition at equilibrium was fixed by the relative temperatures of the specimen and the reservoir, and by the thermodynamic properties of the system. Upon brine quenching the titanium reaction tube to end a run the vapor pressure of magnesium above the liquid alloys decreased exponentially with decreasing temperature, and the small cross-sectional areas of the holes (4.9 x 10"* sq cm) drastically reduced magnesium losses from the crucibles. Because of its low vapor pressure, germanium losses from crucibles during a run were at most 0.2 mg for pure germanium and correspondingly less for the alloys. This crucible geometry satisfactorily retained the equilibrium alloy compositions on quenching for magnesium-rich (from 3 to 33 at. pct Ge) alloys provided their temperatures were below the melting

Jan 1, 1967

By W. J. Slatosky

As a means of effecting better control of endpoint temperatirres at the Jones & Laughlin basic oxygen furnace plant, a set of mathematical equations has been developed. The eqlutions are the product of a themlochemical anaysis of the process and aye designed to calculate the required scrap, lime, and hot metal additions in terms of a number of independent variables. Results of test heats have warranted adoption of this technique by the Prodrrction Department. BECAUSE of the autogeneous nature of the basic oxygen steel-making process, bath temperature can be controlled without an external fuel supply by charging the furnace with additions that are thermally balanced. The thermal requirements of the charge materials are such that, during the refining process, they throttle the heat generated by the metallurgical reactions in a manner designed to result in a speci-fied temperature at the completion of the heat. In the past, operating personnel at the basic oxygen furnace plant of Jones & Laughlin&apos;s Aliquippa Works relied on their experience and technical knowledge of the process to determine the quantities of charge additions needed to result in a finishing temperature in the range 2880"to 2920" F. (The charge consists primarily of 93 tons of scrap and hot metal plus an amount of lime sufficient to maintain a basicity ratio of 2.8 to 3.2). Estimates of these materials are based on a consideration of the effects on finishing temperature of 1) iron silicon content, having a variation of 0.8 to 1.8 pct; 2) iron temperature, ranging from 2250°to 2600°F; and 3)any excessive cooling of the furnace due to a production delay. The end temperature of the preceding heat also serves as a guide in that, if a heat was within the specified temperature range, the succeeding heat could be charged with materials of nearly the same proportions, provided the hot metal used in each of the two charges was of approximately the same temperature and composition. On the other hand, if a heat was outside the specified tapping range, or if the hot metal used in that heat was of different analysis and temperature from that of the iron to be charged, an adjustment in the proportion of additions is in order for the following heat. Due to the complex thermochemical behavior of the process and to the inexact and subjective nature of the described method of determining charge additions, consistently accurate temperature control was not to be expected. Therefore, those heats out- side the specified tapping range necessitated subsequent adjustments by either reblowing the cold heats for a suitable length of time so as to elevate the bath temperature to the desired level, or cooling hot heats with a proper amount of scrap. Because extra time is required to make these adjustments, production is delayed. In an attempt to devise a method for improving temperature control, an analysis of the thermochemistry of the process was undertaken. This, in turn, led to the development of a set of mathematical equations which enable the calculation of the quantities of scrap, lime, and hot metal needed to result in any specified tapping temperature range. The analysis was not intended to be a repetition of work done by others such as McMulkinl or ~hilbrook.&apos; It was meant to be an extension of their work so that charge additions could be calculated not in terms of silicon alone but, rather, as a function of all independent variables. This paper presents the derivation of these relationships, their effectiveness in controlling bath temperatures, and a method of utilizing them on an operational basis. The Heat Balance—The first step undertaken in the analysis of the problem was the enumeration of the pertinent variables. A list is presented in Table I where it is noticed that these quantities have been separated into the following three categories: important variables, variables considered as constants, and variables to be neglected. The breakdown was an arbitrary one designed to facilitate the analysis; otherwise, the mathematical treatment would have been exceedingly cumbersome and complex. Fortunately, experience has shown that these simplifying assumptions do not seriously impair the accuracy of the calculations. These variables along with the limiting assumptions listed in Table n were then used to write a heat balance of the process by applying the equation of continuity, Rate of Rate of Rate of Increase = Income - Outgo PI ] of Heat of Heat of Heat.

Jan 1, 1962

By K. Tanaka, J. D. Mote, J. E. Dorn

It) an attempt to ulLcoce.lP the operative strain-rate-contl-olliy: dislocation nieclzanistns, specially oviented sizgle clystals of the intel-nzediate 1zexagonal phase containing Ag plus 33 at. pct A1 were tested in tension over a wide range of temperatures. Slip was observed to take place by the {0001} <1120> {l100} mechani fracture took place across the(i100) plane and winning occurred by the (i01Z) ?lechanisn. Basal slip exhibited a strong yield point over the -alzge from 77 to 450°K, the upper ,esolved shear st]-ess having the exceptionally high value of 10,500 psi over this entire ?-a?zge of tenzpei,atuves. The critical 9-esolved shear stress for prismatic slip decreased f7-om 48,000 psi at 4.3"K to 23,000 psi at 170°K (Region 1) follozcirg zt:lzich it decl>eased sloz&ly to 21,500 psi at 475°K (Res&apos;on II); from 475" to 575°K (Regioz III), the c7-itical esolced shear stress dec&apos;-eased precipitously to 2000 psi; and from 575" to 750°K (Region IV) it decreased less afi&apos;dly to a low value of about 500 psi. Pvistintic slip in Region I was pobably controlled by the tliel-nally activated riecharzisui of nucleation and g,-ozcth of kinks in dislocations lying in Peierls potential troughs. In Region II for prismatic slip the critical 1-esolved shear stress was slzocn to be deteemined by sh0l.t-range 01-dering, Overall the forgiorz fo basal slip, 7.c.lre1-e a Strong yield-point phenorlienu ia7as observed, the critical vesolved slzea?-stress was shoztn to be determined by n conibirzation 0-f Szizuki locking and short-range-order Izavderzizg, The precipitous decrease in the critical resolved shear stress with increase in ter,/pe7-atrir-e over Region HI was tentatively ascribed to a decrease in the degree of slort-)ange 07-del;iqq (0)- clusteing) and also the effect of fluctuations the degree of o?der, It is at pgreser2t zrtzce)taitz as to 1t1hethe1- these or other possi1)le effects are also ,esponsible. fo- the data obsel-ved 172 Region IV. 1NTEREST in inter metallic compounds stems not only from their role in dispersion hardening of polyphase alloy ystems but equally from their potentialities for high strength, hardness, and stability not only at atmospheric temperatures but especially at elevated temperatures. As summarized in a re- cent symposium of the Electrochemical Society on "Mechanical Properties of Inter metallic Compound", most of the experimental evidence regarding the mechanical behavior of intermetallic compounds centers about the effect of temperature on the hardness and ductility of polycrystalline specimens. The available data reveal that the plastic behavior of intermetallic compounds might be rationalized in terms of the usual dislocation mechanisms appropriate to a solid solutions providing the additional complexities arising from crystal structure, long-range ordering, short-range ordering, and defect lattices are taken into consideration. It is apparent, however, in terms of the history on a solid solutions, that a complete detailed mechanistic rationalization of dislocation processes may not be possible until the deformation processes are studied in single crystals of intermetallic compounds. The present paper contains a preliminary report on the plastic behavior of single crystals of the hexagonal Ag-A1 intermetallic phase over a wide range of temperatures. The results confirm the thesis that single crystal data provide a most effective method of identifying operative dislocation mechanisms in intermetallic compounds. EXPERIMENTAL TECHNIQUES Several factors prompted the selection of the hexagonal Ag-A1 intermetallic phase for this preliminar investigation on the plastic properties of single crystals of intermetallic compounds: 1) This phase has a wide solubility range5 which would permit future investigations on the effect of composition and axial ratios on slip mechanisms. 2) Although it undoubtedly exhibits short-range ordering (or clustering) this intermetallic phase is free from complexities arising from long-range ordering.6 3) Since the atomic radii of aluminum and silver are practically identical, the possible complications due to Cottrell locking are minimized. 4)Whereas the dislocations on the basal planes are expected to dissociate into Shockley partials and are thus susceptible to Suzuki locking, those on the prismatic planes probably remain complete. 5) The axial ratio, being 1.61, is almost ideal, suggesting that short-range ordering may be almost spherically symmetrical. The present investigation was conducted exclusively with the hexagonal Ag-A1 alloy containing 33 at. pct Al. Preliminary investigations revealed that this alloy undergoes basal slip by the (0001)

Jan 1, 1962

By Peter R. Morris

The effecl of preferred orienlation on X-vay dzffvaction measurements of retained austenzte was investigated for four precipitation-hardening staznless steels in sheet form. A method is preserzted for estimating the ervor in measurement associated with a given samplirig direction. The method was used to select an "optimum" sampling direclion in order to minimize errors in measurement due to preferred orientation. hleasuremenls of retained austenite content employing lhe proposed sampling direction are conzpaved to measuretnents enzploying the more commonly used normal direclion for a series of sawzples. THE first application of X-ray diffraction to the measurement of retained austenite in steels is due to Sekito, 1 who employed a photographic technique in which the (111) reflection from a thin strip of gold affixed to a cylindrical sample was employed as a standard. Averbach 2 introduced the "direct comparison" method in which the ratios of observed to calculated random intensity are assumed proportional to the austenite and/or martensite contents. Averbach&apos;s work forms the basis of most subsequent X-ray diffraction methods for the determination of retained austenite. Subsequent improvements are due to: Averbach and Cohen,3 who employed a sodium chloride crystal to monochromate cobalt radiation; Averbach et a1.,4 who introduced a bent sodium chloride monochromator; Mager,&apos; who used a bent quartz crystal to monochromate chromium radiation ; Littmam, who first used a geiger counter diffractometer for this purpose; Beu and Beu and Koistinen, 11,12 who studied effects of absorption factor, surface preparation, sample geometry, integrated intensity vs peak height, choice of radiation, monochromator, and filter. The possibility of errors in measured values due to orientation effects was noted by Miller,13 who suggested examination of a surface other than the plane of rolling. Lopata and Kula 14 have developed an experimental technique in which the preferred orientation is measured in each sample. They illustrated the method for a sample containing 42 pct retained austenite. Application of their technique to the 1 to 15 pct range typical for the precipitation-hardening stainless steels does not appear feasible. EXPERIMENTAL PROCEDURE The nominal compositions of the precipitation-hardening stainless steels investigated are listed in Table I. Ingots were solution-treated, hot-rolled to approximately 0.2 in., and reduced to 0.050 in. by a suc- cession of cold rolling and annealing operations. After this treatment the 17-4PH sample was in the marten-sitic condition, while the 17-7PH, PH 14-8Mo, and PH 15-7Mo samples were in the austenitic condition. Samples of 17-7PH and PH 15-7Mo steels in the mar-tensitic condition were obtained by heating to 1750&apos;F for 10 min and holding at -100°F for 8 hr. A sample of PH 14-8Mo steel in the martensitic condition was obtained by heating to 1700°F for 1 hr and holding at -100°F for 8 hr, followed by aging at 950" for 1 hr. POLE FIGURE DETERMINATIONS Samples were thinned to 0.003 to 0.005 in. by etching in a solution containing 250 ml reagent-grade phosphoric acid (85 to 87 pct H3PO4), 250 ml technical-grade hydrogen peroxide (30 to 35 pct H 2 O 2), and 50 to 100 ml reagent-grade hydrochloric acid (37 to 38 pct HCl). The specimens were placed in an "integrating" sample holder which provided a 1-in. oscillation in the plane of the sample. The diffractometer was aligned to measure the intensity diffracted by planes of the particular {hkl} type being studied. The sample was Set for a given latitude angle, a, measured from the plane of the sheet, and diffracted intensity recorded as the longitude angle, 0, measured in the plane of the sheet from the rolling direction, was increased from 0 to 360 deg. After a 360-deg scan of B, a was incremented by 5 deg, and the process repeated. Random standards obtained by spraying suspensions of powdered iron (bcc structure) and nickel (fcc structure) in lacquer were used to correct observed intensities for absorption and geometrical effects. Zirconium-filtered molybdenum radiation was used to determine the transmission regions of the (111) (0to 45 deg), (200) (0 to 60 deg), and (220) (0 to 45 deg) austenite and (110) (0 to 45 deg), (200) (0 to 50 deg), and (211) (0 to 35 deg) martensite pole figures. Vanadium-filtered chromium radiation was used to

Jan 1, 1968

By B. H. Kear, B. J. Piearcey

The orientation and temperature dependence of the tensile and creep propevties oj Mav-M200 crystals halle been determined. Crystals oriented for single slip exhibit ,maximum ductility, minimum work hardening, and least creep resistance, whereas crystals in multiple slip orientations show nzinimu~n ductility, strongest work hardening, and greatest creep resistance. At 1400" and 1600°F there is a marked improzlenzent in creep strength for orientations approaching [001] and [111], indicating that interactions between dislocations gliding in intersecting octahedral slip systems play an important role in creep resistance. At 1800°F the creep strength is much less dependent on orientation, which is rationalized in terms of slip in cube planes as well as octahedral A frequent mode of failure in high-strength cast nickel-base superalloys is by intergranular fracture, particularly along those grain boundaries oriented transverse to the major stress axis. VerSnyder and ~uard&apos; demonstrated that this problem could be overcome by eliminating transverse grain boundaries through unidirectional solidification. Piearcey and versnyder2 made use of this principle in the development of unidirectionally solidified gas turbine blades and vanes, where the growth direction of the columnar grain structure coincides with the axis of principal stress under operating conditions. The present investigation was undertaken to determine if further improvement in properties may be obtained by eliminating grain boundaries altogether, so as to take advantage of the well-known dependence of mechanical properties of single crystals upon the orientation. 1) EXPERIMENTAL PROCEDURE Single crystals of Mar-M200* were grown from the melt under vacuum by a modified Bridgman method. The melt was poured into a preheated alumina mold, and crystal growth was promoted from one end by appropriate gradient cooling. Tensile and creep specimens (2 in. diam by $ in. gage length) were prepared by a series of operations involving electrical discharge machining, precision grinding, and electropolishing. The orientations of the specimens were determined by the Laue X-ray back-reflection method. Tensile tests were carried out in aWiedemann machine with furnace attachment, using a strain rate planes. In all orientations imzpvouement in the strength charactevistics of the material can be induced by heat treatment. Creep ad stress rupture data for (001) oriented crystals are compared with similar data obtailted previously joy random polycvystalline material, and also columnar grained material having a prejevved (001) orientation. The single-crystal )material exhibits both longer rupture life and lower minimum creep rate at all temperatuves, and the rupture elongation is comparable with that in the columnar grained material. From these results it is concluded that single crystals should and useful application in gas-turbine blades and tanes. The optimum orientation for a blade is considered to be with its axis of principal stvess parallel to (001) ou (111). of 0.0001 sec-&apos;. Load and extension were recorded directly on an X-Y recorder. The strain measuring device consisted of extension arms attached to the grips at one end and leading out of the furnace to an LVDT (linear variable differential transformer) at the other. Creep tests were performed using a standard constant load creep frame. 2) DISCUSSION OF RESULTS 2.1) Structure of Alloy. The structure and segregation in as-cast and heat-treated Mar-M200 has been described in detail else where.~ The main features are as follows: the as-cast material is heavily cored, due to pronounced dendritic segregation during solidification; the dendrites are rich in tungsten and cobalt whereas the interdendritic regions are rich in chromium, titanium, nickel, and carbon. The structure consists of -60 vol pct coherent precipitate of y&apos;, basically Ni3(A1,Ti), in a matrix of y (nickel-base solid solution), interspersed in the interdendritic regions with minor MC carbides and -y&apos; eutectic. The y&apos; particles, and y-y&apos; eutectic, contain more titanium, aluminum, and nickel, and less tungsten, cobalt, and chromium than the y matrix. Heat treatment partially removes segregation, eliminates the eutectic, refines the y&apos; dispersion in y, and gives additional partially coherent M23Cs carbide. An as-cast crystal, therefore, is composed primarily of two oriented phases (y + y&apos;), whereas the normally heat-treated crystal consists of three oriented phases (y + y&apos; + MZ3Cs). Typical electron transmission micrographs of the y + y&apos; structure are shown in Fig. 1. Crystals grown in the (100) orientation develop a simple unidirectional dendritic structure, Fig. 2, since (100) happens to be the preferred direction of growth for dendrites in this material. Crystals grown in the {110) and (111) orientations, however, tend to promote equal growth, generally in separate colonies, in the two and three geometrically favored (100) growth directions, respectively. In other orientations of growth, a single (100) dendrite direction generally pre-

Jan 1, 1968

By B. Chalmers

THE practical importance of the phenomena of melting and freezing must have been recognized for a very long time. The difference between ice and water, for example, has had a profound influence on the history of mankind and the evolution of society. The possibility of melting a metal and allowing it to freeze in a mold of chosen shape has been an essential ingredient in our mastery of the art of shaping metals, and therefore in the evolution of the: machine age in which we find ourselves. The importance of melting and freezing, as applied to metals and alloys, has been so great, in fact, that empirical solutions have been found for the multitude of practical problems that have arisen. This approach has been so successful that relatively little attention has been directed to arriving at an understanding of the fundamentals of the processes. But metallurgy has come to a stage at which we may expect that some, at least, of the more complex problems that have not yet been solved (or perhaps even recognized) may be handled more effectively by scientific study, theoretical understanding, and logical experimentation than by trial and error. In this lecture, therefore, I propose to describe in outline what I think really happens when a metal freezes. In doing so I hope to explain many of the phenomena which have been observed, and in particular to account for the structures that are obtained in actual ingots and castings. The basic problem, to which this lecture represents a tentative partial answer, is this: a mass of metal, containing known proportions of various elements, is melted, heated to a given temperature, and then allowed to freeze under specified conditions. What will be the "structure" of the resulting metal? The term structure includes: 1—crystal size, shape, and orientations, 2—distribution of chemical elements, and 3-—shape, including cracks, cavities, pores, etc. The Solid-Liquid Interface We will first consider what takes place if a single crystal of a metal in the form of a rod is heated, not uniformly, but so that one end is hotter than the other. If this heating process is continued long enough, the hotter end will eventually melt; we will suppose that the rod is in a containing vessel so that the molten metal does not run away, Fig. 1. When some of the metal has melted, we have some solid, some liquid, and an interface or surface of contact between them. If the source of heat is now removed, the interface will move so that some of the liquid freezes, and if the supply of heat is suitably adjusted the interface will remain at rest. This very simple arrangement allows us to study the basic processes of melting and freezing, and if we fully understand this simple case, we may be able to account for what takes place under practical conditions where the heat does not all flow in the same direction, and where the heat flow is determined not by a controllable source of heat but by the heat capacity and temperature of metal and mold, and by the heat loss from the mold surface. The solid-liquid interface is evidently the region of the greatest interest to us; on one side of it there is crystalline solid, and on the other, liquid. In the solid, each atom has a well defined position, around which it vibrates as a result of thermal agitation. It only leaves this position in the relatively rare event of a "diffusion jump." The liquid is much less systematically organized. The atoms are about as far from their neighbors as in the solid, but the arrangement is much less systematic and is continuously changing. The solid and the liquid are represented diagrammatically in Fig. 2. The average energy of the atoms in the liquid is greater than in the solid by an amount that corresponds to the latent heat of fusion, i.e., the amount of heat that has to be supplied to convert unit mass of solid into liquid at the same temperature. The Two Processes As has recently been shown by Jackson and Chalmers,3 many of the features of the processes of freezing and melting can be understood if it is assumed that a continuous and rapid interchange of atoms between solid and liquid always takes place at a solid-liquid interface." It is necessary to con- sider two distinct processes, that of melting, in which atoms leave the surface of the solid and become part of the liquid, and the converse process,

Jan 1, 1955