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By L. D. Fetterolf, G. T. Mahler, W. M. Peirce, R. K. Waring

UNTIL recently, the only commercial method of producing magnesium has been fused salt electrolysis, despite a considerable amount of experimental work on the direct reduction of magnesium oxide. In this early work, a number of investigators demonstrated that magnesium oxide would react with any one of several reducing agents to produce magnesium vapor, but that the mixture of magnesium oxide and reducing agent must be heated to a high temperature even in a vacuum. In particular, it was demonstrated that silicon and aluminum are effective reducing agents and that when either of these is used the magnesium vapor can be condensed to massive metal. In spite of this knowledge, no successful commercial reduction process was developed, at least in this country, because of the operational difficulties imposed by the requirement of high temperature and vacuum and because of the high cost of the reducing agent. The outstanding experimental work done by Pidgeon, who carefully reviewed all of the known methods of making magnesium and then selected ferrosilicon reduction, overcame some of the operational difficulties. The process developed by Pidgeon comprises briquetting a mixture of calcined dolomite and reducing agent, pre-heating the briquets to about 600°C. in an externally heated alloy retort, reducing the MgO with silicon in an evacuated horizontal alloy retort heated externally to about 1150°C., and condensing the magnesium vapor to a solid in a cold extension of the retort projecting beyond the fr6nt of the furnace. A major advantage of Pidgeon's process is that the retort is not cooled down between charges. Earlier investigators had used apparatus that necessitated cooling and reheating of the retort between charges. Early in January 1942, when the War Production Board was considering the Pidgeon process for quickly increasing the production of magnesium, The New Jersey Zinc Co. offered to have a research investigation of the process carried on, with the hope of assisting in its further development. This offer was accepted, and a two-retort pilot plant was built at Palmerton and put in operation on Jan. 29, 1942. An intensive investigation of certain phases of the process was carried out in the ensuing four months. This investigation was completed in the last part of May 1942, and the pilot plant was then shut down. Subsequently, The New Jersey Zinc Co. was requested to have further development work done on the process, and a more extensive investigation was undertaken in August I942 under contract with the War production Board and under the super- vision of the War Metallurgy Committee. This paper describes the phases of the investigation that are thought to .be

Jan 1, 1944

By Lawrence Veiller, D. Eppelsheimer

D. Eppelsheimer, * Middletown, Ohio.—The housing of employees has so many and so varied aspects that in order to reach even an approximately correct solution it is necessary to have in mind a few fundamental principles; but it is not possible as yet to write these housing principles in the clear and correct form that is possible with many of our natural laws. Manifestly, the problem depends first on the kind of people it is necessary to house. What is suitable for the Southern unattached negro is not suitable for the married skilled American. The influx of colored labor has affected quite a number of what were satisfactorily housed communities. The second important factor is the relative proportion of the number of employees to the total employable population of the community in which the industry is located. The employer of a hundred men in a large city has little responsibility in the matter of housing his employees. If he employs 75 per cent. of the employable population in a community of 27,000, as is the case of the company with which the writer is connected, it means a large responsibility. In the establishment of an entirely new plant in a more or less isolated place, the responsibility becomes greater. As engineers, we design and write the specifications for the machinery to accomplish a definite purpose, and proceed to house it, provide the necessary buildings with their accessories in the way of cranes, or heating systems, or sprinkling systems, as the case may be. There is no reason why the operating force should not be built up in very much the same way: design the organization, write its specifications so that the employment department can secure the proper men, and then house that organization with just as much thought and care as is given the plant. In the plant, the various machines will work along certain definite lines and accomplish certain results; but even if we start with the proper organization it takes considerable time to get that organization working together. One of the most important elements to this end is the proper housing of the organization. A man usually spends more time at home than at work. Proper surroundings and a comfortable, convenient house of good appearance exercise an influence that cannot be denied, and an employee situated in such surroundings is far more inclined to follow the policies of his employer and take an active part in furthering them than one dissatisfied with his home and surroundings, which feeling

Jan 1, 1919

By F. Louis Grammer

THE difference between blast-furnace gas and ordinary producer-gas is chiefly that blast-furnace gas is richer in CO, and poorer in hydrocarbons and hydrogen, as is shown in Table I. TABLE I.-Volume-Composition of Producer-Gas and Blast-Furnace Gas.. Producer-Gas. Blast-Furnace Gas. Per Cent. Per Cent. (Volume.) (Volume.) CO . 22 to 33 25.5 00., . 6 to 3 13.0 H . . 13 to 7 1.5 CH, 3 to 1.5 0.0 N . 54 to 60 60.0 If natural gas, water-gas, or by-product coke-oven gas be available, blast-furnace gas can be made to resemble very closely in calorific value the average producer-gas by merely mixing in one of these products, which are richer in hydro-carbons and, hydrogen. Blast-furnace gas, however, possesses a virtue which is sometimes absent in producer-gas, especially with coals very high in sulphur-namely, that blast-furnace gas is relatively free from sulphur. In some regions the sulphur in coal is an acute problem, and it is highly desirable to find uses for the products which are specially high in sulphur-content. An advantage would be gained if coal was coked before charging into the gas-producers, but this adds to the expense. Sulphur may be partly eliminated from coal by washing it, the success depending upon the form in which the sulphur occurs, and upon the efficiency of the washer, but it cannot always be removed to the extent desired at most American plants. It is not practicable to remove all the sulphur from producer-gas by washing it, though Mr. Reinhardt, of Germany,

Sep 1, 1908

By Floyd C. Kelly

A. HUltgren, .Söderfors, Sweden (written discussion*).—From the results obtained in his own experiments as well as those of Austin and of Grube Mr. Kelley derives a general law, expressed tentatively in the following words: "whenever two metals are brought into intimate contact at a temperature at which diffusion takes place, a comparatively rapid, or abnormal, grain growth results." It is suggested that,, in order adequately to represent the facts, this definition should he restricted by the following qualifications: a and b are the two metals, b diffusing into a. A. At the temperature in question a should exist as phase a 1 having a limited solubility for b. B. The supply of b by diffusion should be sufficient, in view of the rate of diffusion into a 1, to increase the concentration of b above the saturation value in a 1 so as to cause a new phase a2 to form. (7. The phase a2 should have a range of solubility for 6, thus rendering continued diffusion possible. D. In order that the columnar grains may be preserved in the structure the phase a2 should, of course, not suffer transformation on cooling. The phenomenon thus defined may be described as progressive transformation by diffusion. Its mechanism would appear to he as follows: Fig. 17 shows a portion of the equilibrium diagram a-b, Fig. 18 the distribution of b in solution after various periods of diffusion, Fig. 19 represents the structure in cross-section of a cylindrical rod of a at the end of heating period 3. 1. The first effect of diffusion of b into a will be to establish a concentration gradient in phase a1 (1, Fig. 18). When the saturation value for the temperature of the experiment (m, Fig. 17) is reached at the surface, nuclei of, a2 of composition n will form here, and later develop into a continuous layer. Assuming that diffusion proceeds without irregularities and that transformation at any point sets in without lag—i. e., in the moment saturation is exceeded—the transformation a1-a2 will advance inwards on a cylindrical surface concentric with the surface of the rod. The discontinuity of composition at the transformation surface in the position it happens to have at the end of the treatment (3, Fig. 18) will be preserved at room temperature, if the cooling is not particularly slow, and be recorded in the structure as a marked, smooth line, in agreement with Grube's and the author's observations. The shape of the distribution curves in Fig. 18 is also corroborated by the analyses given by Grube. 2. During diffusion, since the secondary phase a2 is always in immediate contact with the saturated part of the primary phase a1, there should be very little lag in the transformation. This means that the first a2 grains formed should grow in preference to the formation of independent nuclei; in other words, columnar growth results. It does not seem necessary to assume, with Green,' whose conception of the phenomenon

Jan 1, 1929

By Floyd C. Kelly

A. HUltgren, .Söderfors, Sweden (written discussion*).—From the results obtained in his own experiments as well as those of Austin and of Grube Mr. Kelley derives a general law, expressed tentatively in the following words: "whenever two metals are brought into intimate contact at a temperature at which diffusion takes place, a comparatively rapid, or abnormal, grain growth results." It is suggested that,, in order adequately to represent the facts, this definition should he restricted by the following qualifications: a and b are the two metals, b diffusing into a. A. At the temperature in question a should exist as phase a 1 having a limited solubility for b. B. The supply of b by diffusion should be sufficient, in view of the rate of diffusion into a 1, to increase the concentration of b above the saturation value in a 1 so as to cause a new phase a2 to form. (7. The phase a2 should have a range of solubility for 6, thus rendering continued diffusion possible. D. In order that the columnar grains may be preserved in the structure the phase a2 should, of course, not suffer transformation on cooling. The phenomenon thus defined may be described as progressive transformation by diffusion. Its mechanism would appear to he as follows: Fig. 17 shows a portion of the equilibrium diagram a-b, Fig. 18 the distribution of b in solution after various periods of diffusion, Fig. 19 represents the structure in cross-section of a cylindrical rod of a at the end of heating period 3. 1. The first effect of diffusion of b into a will be to establish a concentration gradient in phase a1 (1, Fig. 18). When the saturation value for the temperature of the experiment (m, Fig. 17) is reached at the surface, nuclei of, a2 of composition n will form here, and later develop into a continuous layer. Assuming that diffusion proceeds without irregularities and that transformation at any point sets in without lag—i. e., in the moment saturation is exceeded—the transformation a1-a2 will advance inwards on a cylindrical surface concentric with the surface of the rod. The discontinuity of composition at the transformation surface in the position it happens to have at the end of the treatment (3, Fig. 18) will be preserved at room temperature, if the cooling is not particularly slow, and be recorded in the structure as a marked, smooth line, in agreement with Grube's and the author's observations. The shape of the distribution curves in Fig. 18 is also corroborated by the analyses given by Grube. 2. During diffusion, since the secondary phase a2 is always in immediate contact with the saturated part of the primary phase a1, there should be very little lag in the transformation. This means that the first a2 grains formed should grow in preference to the formation of independent nuclei; in other words, columnar growth results. It does not seem necessary to assume, with Green,' whose conception of the phenomenon

Jan 1, 1929

By Tracy L. Atherton

The mapping of slant-hole oil fields is complicated by the fact that relationships between wells are subject to variations in three dimensions and are not readily adaptable to representation on a plane surface. Formalized perspectives usually expand into an undecipherable maze of lines and peg models with the necessary supporting dividers serve only to awe the beholder with their perplexity. The usual compromise arrived at is a plotting of the projection of the courses of all of the wells in the field onto a horizontal plane (Fig. I). These complicated plots, when used in conjunction with the individual vertical projections of the wells, heretofore have been the most practical foundation for the study of general field problems. This method has many shortcomings, however, which arc not found in the recently developed straight-hole equivalent projec-tion method. The new method supplies a series of maps similar to the type now in common use in straight-hole fields. It is remarkably simple to use and supplies a ready check on clearances between wells. Perhaps the method can best be understood if the steps that led to its development are described. Common practice of oil-well surveyors is to supply the owner with a tabling of the survey and a plan view plotted against the true meridian. If a vertical projection is plotted, it is usually plotted separately and shows vertical depths against the projection of the stations along a section line joining the top and bottom of the hole on the plan view. A more practical method would be to plot the section line of the plan parallel to the abscissa of the vertical projection (Fig. 2). If this is done, any line parallel to the "base line1' will pass through the points on each projection that represent a single point in the hole. Another very useful graph, which the well surveyor could provide, would be plotting of vertical depths against measured depths. Fig. 3 illustrates the next step facilitated by this form of plotting. The lines designated "well A" represent the proposed course of a hole to be drilled. Superimposed on the drawing, in its proper relative position, is the plan view and a portion of the vertical projection of a present producer, well B." From an inspection of the plan view we arrive at the correct conclusion that the only indicated possibility of collision is at the point of crossing of the wells on the plan view. Referring to the vertical projection, note that the vertical depths of stations on B, in the vicinity of the crossing, are plotted on the same plane of projection as A. The clearance is the indicated distance between the two vertical sections measured along the parallel to the "base line," which passes through the point of intersection of the plan view. Repeat this process for the other wells crossing the proposed course of A on the plan view and you have a preliminary check of clearance for the proposed course. A similar comparison of crossings on the vertical projections of all >

Jan 1, 1941

By Tracy L. Atherton

The mapping of slant-hole oil fields is complicated by the fact that relationships between wells are subject to variations in three dimensions and are not readily adaptable to representation on a plane surface. Formalized perspectives usually expand into an undecipherable maze of lines and peg models with the necessary supporting dividers serve only to awe the beholder with their perplexity. The usual compromise arrived at is a plotting of the projection of the courses of all of the wells in the field onto a horizontal plane (Fig. I). These complicated plots, when used in conjunction with the individual vertical projections of the wells, heretofore have been the most practical foundation for the study of general field problems. This method has many shortcomings, however, which arc not found in the recently developed straight-hole equivalent projec-tion method. The new method supplies a series of maps similar to the type now in common use in straight-hole fields. It is remarkably simple to use and supplies a ready check on clearances between wells. Perhaps the method can best be understood if the steps that led to its development are described. Common practice of oil-well surveyors is to supply the owner with a tabling of the survey and a plan view plotted against the true meridian. If a vertical projection is plotted, it is usually plotted separately and shows vertical depths against the projection of the stations along a section line joining the top and bottom of the hole on the plan view. A more practical method would be to plot the section line of the plan parallel to the abscissa of the vertical projection (Fig. 2). If this is done, any line parallel to the "base line1' will pass through the points on each projection that represent a single point in the hole. Another very useful graph, which the well surveyor could provide, would be plotting of vertical depths against measured depths. Fig. 3 illustrates the next step facilitated by this form of plotting. The lines designated "well A" represent the proposed course of a hole to be drilled. Superimposed on the drawing, in its proper relative position, is the plan view and a portion of the vertical projection of a present producer, well B." From an inspection of the plan view we arrive at the correct conclusion that the only indicated possibility of collision is at the point of crossing of the wells on the plan view. Referring to the vertical projection, note that the vertical depths of stations on B, in the vicinity of the crossing, are plotted on the same plane of projection as A. The clearance is the indicated distance between the two vertical sections measured along the parallel to the "base line," which passes through the point of intersection of the plan view. Repeat this process for the other wells crossing the proposed course of A on the plan view and you have a preliminary check of clearance for the proposed course. A similar comparison of crossings on the vertical projections of all >

Jan 1, 1941

By J. C. Bokros

At temperatures above 950°F, zirconium which has been strained a critical amount will experience critical recrystalli-zation. The large grain size thus formed can result in a reduction in the fatigue life by a factor of 2 to a factor of 9 at both high and low temperatures. The critical strains for zirconium vary from 15 pct at 900°F to about 2 pct at 1125°F, while those for zircaloy III vary from 15 pct at 1050°F to 5 pct at 1200°F. Zircaloy II ,experiences no critical recrystallization up to 1200°F. ZIRCONIUM has become increasingly important for nuclear applications and is being employed in reactors at temperatures where recrystallization can occur. Recent work' on the fatigue properties of zirconium has shown that coarse-grained structures developed in zirconium during recrystallization have much lower fatigue lives than fine-grained material. The development of these large grain sizes under such conditions is well known to be the result of critical recrystallization.2-4 Briefly, critical recrystallization occurs when a metal is strained a critical amount and annealed in the recrystallization range. The critical strain is defined as that minimum strain necessary to promote nucleation in the time unit and temperature considered. The maximum grain size occurs at the critical strain, since at this strain the fewest stable nuclei per unit volume grow into new grains. Recrystallization is not evident below this; strain since the nucleation rate is vanishingly lolw, and metal strained more than the critical amount has a higher nucleation rate per unit volume which results in a finer grained structure. This paper describes the critical recrystallization observed in reactor-grade zirconium, zircaloy 11, and zircaloy I11 as a function of annealing temperature and temperature of strain. EXPERIMENTAL The zirconium used was hafnium-free, double arc-melted sponge obtained from the Bureau of Mines. The ingots were forged and hot reduced to 0.08 to 0.10-in. sheet and subsequently cold reduced to 0.035-in. sheet with intermediate and final anneals at 1200 OF for 15 min. The zircaloy II and zircaloy III used were 0.035-in. sheets in the annealed condition. Compositions of these materials as tested are given in Table I. To determine the critical strain at a given temperature, tensile specimens having a0.065-in. taper in a 2-in. gage length were machined from the sheets parallel to the rolling direction. The specimens were polished, etched, and examined metallographically to ensure that all of them were strain-free, initially. Tukon indentations were made every half millimeter along the gage length of each specimen. These served as fiducial marks enabling the plastic strain to be measured with a microscope and micrometer stage. The specimens were pulled to failure at a rate of 0.002 in. per min in an Instron tensile-testing machine. Three temperatures were used for straining: room temperature, 500 ºF, and 900 ºF. The 500º and 900 ºF tests were run in an argon atmosphere. Since the rate of work hardening changes with temperature, a different critical strain was obtained for each temperature of strain. Specimens, prepared in the manner described, were annealed in vacuunl at various temperatures ranging from 900" to 1200 F for up to 1000 hr, after which they were examined metallographically. The critical strain and the recrystallized grain size as a function of strain were determined for each specimen. Results for the same temperature and time indicated that the critical strain measured was reproducible to within 5 pct of each other. RESULTS AND DISCUSSION Since increasing the time of anneal increases the probability of the nucleation of a new grain, the critical strain decreases with time at a decreasing

Jan 1, 1961

By J. D. Hunt, D. T. J. Hurle

A uariety of eutectic structures are formed in faceted/nonfaceted eutectics. The various structures are explained in terms of the absence or presence of small facets in the liquid groove. Regular structures are produced when, for purely geometric reasons facels cannot form. The presence of a facet in the liquid groove leads to the formation of an irregular or a cell-like complex regular structure, due to the relative immobility of the groove. A classification of eutectics was proposed by Hunt and jackson, based on the presence or absence of facets on the primary phases (the absence of facets may be predicted from the dimensionless entropy of melting2). Eutectics were divided into three groups: 1) eutectics in which both phases grow in a nonfaceted manner; 2) eutectics in which one phase grows faceted, the other nonfaceted; 3) eutectics in which both phases grow faceted. It was suggested that regular1 rodlike or lamellar structures1 should be formed in the first group, that irregular or complex regular structures1 should be formed in the' second, and that irregular structures1 should be formed in the third. Recently it has been shown that the structural classification is incomplete. Regular rodlike structures (InSb-NiSb eutectic3), or broken lamellar structure (Bi-Zn eutectic, Fig. 8), are formed in alloys of the second group when the faceted phase has a large volume fraction. Hunt and jackson' argued that regular structures could form in faceted/nonfaceted systems, but that such structures would be unstable in the presence of microfacets on the lamella of the faceting phase, because the growth rate at a point on such a facet would depend on the kinetic undercooling at the point of nu-cleation on the facet, and not on the local kinetic undercooling. In these circumstances it would not be possible to consistently balance the compositional and kinetic undercooling over a lamellar structure and thus obtain a stable isothermal interface. In this paper we discuss in detail the origin of the various structures formed in faceted/nonfaceted systems, pointing out that the most important factor promoting the formation of a regular structure is the absence of a facet in the liquid groove. 1) FACET FORMATION IN SINGLE-PHASE MATERIALS Facets form when there is an energy barrier for the addition of a new solid layer on an existing solid. When a barrier is present,2 growth proceeds by the lateral movement of steps across a crystallographic plane. The rate-controlling stage of the process occurs when the step is first formed. Hulme and Mullin6 have shown that faceting in single-phase materials can only occur when both interface curvatures are convex with respect to the solid and when the surface is tangential to the facet plane. When even one of the curvatures is concave a facet does not form because new layers of solid from adjacent regions can always feed the facet plane, Fig. 1. Growth under these conditions is then as easy as elsewhere. Similar considerations will apply to eutectic growth; consequently the shape of the faceted phase is extremely important. 2) LAMELLAR SPACING CHANGES IN EUTECTICS Jackson and Hunt7 have shown that the interface undercooling AT of a growing lamellar interface (neglecting kinetic undercooling) is related to the lamellar spacing, A, and growth velocity, v, by an expression of the form: where m, Ql, and nL are constants of the system given in Ref. 7. Eq. [I] is plotted for fixed v in Fig. 2. Jackson and Hunt postulate that a regular eutectic grows near, but to the right of the minimum in the AT vs A curve. They argue that the spacing cannot be to the left of the minimum because the interface is then unstable to fluctuations in A. It cannot grow too far to the right, because when the spacing becomes too wide an isothermal interface can no longer be maintained over the large-volume-fraction phase.7 It is argued that during any change in growth rate the lamellar spacing remains in the permitted range by the movement of lamellar faults. When the spacing is too wide, the fault, shown in Fig. 3, moves to the left; when the spacing is too narrow it moves to the right. The faults, however, have to be formed. heir formation has been shown to occur when local regions deviate considerably from the spacing defined by the lamellar When the spacing is locally too narrow (it passes to the left of the minimum, Fig. 2), pinching off of the narrow phase occurs. When the spacing is locally too wide, the interface on the large volume-fraction phase can no longer be maintained as an iso-

Jan 1, 1969

By Gail F. Moulton

The production of petroleum in Illinois in 1928 was approximately 6,500,000 bbl., a decline of about 500,000 bbl. from the previous year and of about 1,500,000 bbl. from 1924. Production increased about 200,000 bbl. in Indiana to slightly less than 1,000,000 bbl. Production for 1929 is estimated at approximately 6,000,000 bbl. for Illinois and 1,000,000 bbl. for Indiana. Illinois Because production from most of the wells in the state has declined to a small daily average and the low prices for crude oil discouraged wildcatting, the number of wells drilled fell below that for any previous year since the development of commercially important production in the state. The Ohio Oil Co. discovered a pool of apparent commercial importance in southwestern Illinois near Dupo, in St. Clair County, and favorable showings of oil were encountered in a well in southeastern Illinois, near Harrisburg in Saline County. New production from the Dupo area is expected to check the rate of decline for the state. Thc following tablel summarizes field developments for 1927 and 1928 (for important detail by counties see notes at foot of table): 1027 1928 Completions........................................... 162 145a Initial production, bbl.................................. 2244 1840b Dry holes........................................,.... 66 58" Gas well completions................................... 13 8d 0111 wells abandoned.................................... 45" a Crawford, 44; Lawrence, 28; Wabash, 40. b Crawford, 501; Lawrence, 403; St. Clair, 165 (4 completions); Wahash, 668. o Crawford, 12; Wabash, 19. d Crawford, 6. b Lawrence, 21; Wabash, 15. The discovery well in the Dupo field in St. Clair County, produced about 150 bbl. per day from the Trenton lime at 660 ft. It is located in a northern extension of the Columbia-Waterloo anticline on which the Waterloo pool was developed in 1921. The best information on the.

Jan 1, 1929

TULSA, the host of the Petroleum Division this year, is the oil metropolis of the Mid- Continent and gateway of the Southwest. It has risen in less than three decades from a dusty cattle town of less than 1000 population to its present-day status of a modern, wide-awake and prosperous city of close to 150,000, with an assessed realty valuation of approximately $100,000,000. Oil was discovered near Tulsa in 1901, and with it came th.2 development of the Mid-Continent field, one of the richest in the world. Tulsa from the start has been the center of operations, and its location on foul- and aggressive application of the airplane to oil-field requirements tends to fix this status as production is developed farther and farther afield. That Tulsa is far more than an ephemeral oil town is punched into the newcomer's- especially the Easterner's-mind, as he is whisked by taxi from the railroad station to the Hotel Mayo. The cicadalike pounding of the riveters on the steel skeletons of many skyscrapers, mounting upward to fill the gaps in an already well-developed skyline, dispels the feeling of a new atmosphere and puts him back on Forty-second Street, Michigan Boulevard or whatever his own particular "Main Street" may be along which an American city is being remade. Practically every company of any importance operating in the Mid-Con-

Jan 1, 1928

By Jos. Van Ackeren

Although the Siemens regenerator principle was introduced into byproduct coke-oven design about 40 years ago, many problems of construction, and particularly of heat distribution and pressure conditions, have not been fully solved. Heat should be applied to the walls of a coke oven in such a way that the coking of the charge of coal will be completed everywhere at the same time, and at approximately the same temperature. This means that the application of heat should be uniform from the top to the bottom of the coal mass (except for the thin layer at the top that is purposely kept at a somewhat lower temperature to reduce cracking of the byproducts); also that a little more heat must be applied to the coke end than to the pusher end, because the coal mass is a little thicker at that end. As a modern coke oven is about 40 ft. long and 12 ft. high, a real problem is involved in the proper application of heat to the oven walls so as to secure quick coking time (without endangering the walls through local overheating) and produce coke made at a uniform temperature. Design of Ovens In all regenerative ovens, the points of combustion are arranged in duplicate sets, one set operating in one-half the area of the heating wall and the other set alternately operating in the other half. Because of the reversal of the flow of gases, the points of maximum and minimum temperatures are alternately located at the same places, thus preventing dangerous local overheating. The practicability of the principle of reversal of flow seems to have been recognized at an early date, and has been applied with every conceivable flue arrangement, combustion chamber, and means of air and gas supply. To summarize the various principles that have proved useful for the control of oven-wall temperature, the best practice seems to have resulted from the acceptance of the use of vertical flues; the separate supply of air and gas to the base of these flues, with the resulting flame

Jan 1, 1923

By Jos. Van Ackeren

Although the Siemens regenerator principle was introduced into byproduct coke-oven design about 40 years ago, many problems of construction, and particularly of heat distribution and pressure conditions, have not been fully solved. Heat should be applied to the walls of a coke oven in such a way that the coking of the charge of coal will be completed everywhere at the same time, and at approximately the same temperature. This means that the application of heat should be uniform from the top to the bottom of the coal mass (except for the thin layer at the top that is purposely kept at a somewhat lower temperature to reduce cracking of the byproducts); also that a little more heat must be applied to the coke end than to the pusher end, because the coal mass is a little thicker at that end. As a modern coke oven is about 40 ft. long and 12 ft. high, a real problem is involved in the proper application of heat to the oven walls so as to secure quick coking time (without endangering the walls through local overheating) and produce coke made at a uniform temperature. Design of Ovens In all regenerative ovens, the points of combustion are arranged in duplicate sets, one set operating in one-half the area of the heating wall and the other set alternately operating in the other half. Because of the reversal of the flow of gases, the points of maximum and minimum temperatures are alternately located at the same places, thus preventing dangerous local overheating. The practicability of the principle of reversal of flow seems to have been recognized at an early date, and has been applied with every conceivable flue arrangement, combustion chamber, and means of air and gas supply. To summarize the various principles that have proved useful for the control of oven-wall temperature, the best practice seems to have resulted from the acceptance of the use of vertical flues; the separate supply of air and gas to the base of these flues, with the resulting flame

Jan 1, 1923

By A. Totani, S. Nakajima, H. Okazaki

The phase diagram for the SnTe-SnSe system has been studied in the temperature range from 300° to 900°C by differential thermal and quenching techniques. The X-ray measurements were made on quenched specimens. High-temperature diffraction was also made to study the phase transition in SnSe. The system is proved to be of a eutectic type in which no intermetallic compound exists. The eutectic point is at the composition SnTeo.55 Seo.45. the eutectic temperature being 755°C. Solid solubility limits are SnTeo.6Seo.r and SnT eo. 3s Seo.6s at the eutectic temperature, and change almost linearly to SnTeo.aaSeo.lz and SnTeo.18 Seo.az as temperature decreases to 300°C. It was shown that the SnSe phase has a phase transition of the second order at about 540°C and that the transition temperature decreases with increase of the SnTe content. THERMOELECTRIC properties of tin telluride (SnTe) and tin selenide (SnSe) have been studied extensively in recent years. The variation of physical properties with composition could be of interest if these compounds form an appreciable crystalline solution. The purpose of present investigation is to confirm the formation of crystalline solution or intermetallic compound, if any, and to establish the phase diagram for this system. The crystal structure of SnTe is NaCl type with a cubic unit cell1 (a = 6.313A). The crystal of SnSe having an orthorh2mbic unit cellz (a = 11.496, b = 4.1510, and c = 4.4437A) is isomorphous with tin sulfide (SnS) which has a distorted sodium chloride structure. It has been known that SnSe has a phase at at 540°C; the transition has been assumed to be of the second order. As far as we know, only two studies on the SnTe-SnSe pseudobinary system have been reported. The conclusion obtained in these papers is that, in the composition regions near SnTe and SnSe, the system forms a crystalline solution of the SnTe structure and the SnSe structure, respectively, and that, in the intermediate region, both phases coexist. However, neither the variation of the solid solubility vs the temperature nor the liquidus and solidus were investigated. Hence present writers have attempted to determine the phase diagram of the system by differential thermal analysis (D.T.A.) and X-ray diffraction. EXPERIMENTAL Sample Preparation. Starting materials, SnTe and SnSe, were prepared by the direct fusion of commercially available high-purity (99.999 pct) elements. Stoichiometric amounts of each couple Sn-Te or Sn-Se were weighed into a clear fused silica ampule. After evacuation to a pressure below 10-3 mm Hg, the am- pule was sealed, and annealed at 900°C for 5 hr. The melt was quenched in water. X-ray analysis confirmed the formation of a single phase of SnTe or SnSe. The other samples, SnTel-,Sex were synthesized from these SnTe and SnSe by mixing them in the required ratio, followed by annealing at 900°C and quenching. These samples were used directly for D.T.A. For X-ray measurements, samples were annealed at 700°, 600°, or 500°C for 100 hr or at 300°C for 150 hr, and then quenched in water. It was found that the lattice constants of the SnTe phase annealed for 150 hr at temperatures above 500°C did not differ from those annealed for 100 hr at the same temperatures. However the X-ray phase analysis showed that at 300°C the annealing for 150 hr was necessary to attain a true equilibrium state. D.T.A. The solid-liquid equilibrium temperature was determined from D.T.A. measurements. The sample was sealed in an evacuated silica tube and molybdenum powders sealed in an another tube were used as a reference material. The sample and the reference tube were placed in a nickel block and were heated from room temperature to 900°C at a rate of 3°C per min and then cooled down at the same rate to 600°C. Thermocouples for these measurements were Pt-Pt. Rh (10 pct) and the error of temperature measurements was within + l0C. D.T.A. curves were obtained on a two-pen recorder and an automatic controller (PID type) was used for the program of heating and cooling. When temperature reaches the solidus from the low-temperature side, there appears an endothermic peak. The solidus temperature was determined by extrapolation of the straight portion of the starting flank of this peak to the base line. In a similar way, the liquidus temperature was determined from an exothermic peak on D.T.A. cooling curve. In the case of supercooling, if any, its degree can be estimated from the magnitude of the abrupt temperature rise. X-Ray . X-ray powder patterns were taken by a diffractometer using CuK, radiation. Since the SnSe crystal is cleaved easily, the powders become flaky when SnSe-rich samples are ground in an agate

Jan 1, 1969

By E. A. Nesbitt

A new permanent-magnet material has been developed with unusual mechanical as well as magnetic properties. Specimens that have been cast or subjected to a small amount of hot reduction by rolling or swaging may be machined, punched, tapped or drilled. The composition range of the alloys is 30 to 52 per cent iron, 36 to 62 per cent cobalt and 4 to 16 per cent vanadium. After being either quenched, annealed or given the usual cold finishing passes and then heated for 2 hr. at 600°C., such materials have a magnetic energy product of 1.0 X 106 gauss-oersteds. This product is equivalent to that of the well-known Honda steel (36 per cent Co, 4W, 2 Cr, 0.8 C. 0.3 Mn, balance Fe). Material handled in the manner just described does not depend on cold-working for its magnetic properties, and is known as Vicalloy I. The preferred composition for Vicalloy I is 38.5 per cent iron, 52 per cent cobalt and 9.5 per cent vanadium. When the alloys are first hot-worked, then considerably reduced in area by cold-swaging, drawing or groove rolling and then heat-treated, the magnetic energy product measured in the direction of previous extension is increased to 2.0 to 3.5 X 106 gauss-oersteds. These higher values have been obtained only after cold reductions in area of 75 to 95 per cent. Material handled in this manner is known as Vicalloy II and the preferred composi-

Jan 1, 1947

By E. A. Nesbitt

A new permanent-magnet material has been developed with unusual mechanical as well as magnetic properties. Specimens that have been cast or subjected to a small amount of hot reduction by rolling or swaging may be machined, punched, tapped or drilled. The composition range of the alloys is 30 to 52 per cent iron, 36 to 62 per cent cobalt and 4 to 16 per cent vanadium. After being either quenched, annealed or given the usual cold finishing passes and then heated for 2 hr. at 600°C., such materials have a magnetic energy product of 1.0 X 106 gauss-oersteds. This product is equivalent to that of the well-known Honda steel (36 per cent Co, 4W, 2 Cr, 0.8 C. 0.3 Mn, balance Fe). Material handled in the manner just described does not depend on cold-working for its magnetic properties, and is known as Vicalloy I. The preferred composition for Vicalloy I is 38.5 per cent iron, 52 per cent cobalt and 9.5 per cent vanadium. When the alloys are first hot-worked, then considerably reduced in area by cold-swaging, drawing or groove rolling and then heat-treated, the magnetic energy product measured in the direction of previous extension is increased to 2.0 to 3.5 X 106 gauss-oersteds. These higher values have been obtained only after cold reductions in area of 75 to 95 per cent. Material handled in this manner is known as Vicalloy II and the preferred composi-

Jan 1, 1947

By R. H. Richman, F. Borik

A 0.3 pct C-12 pct Cr-6 pct Ni steel was rolled to 93 pct reduclion in area as austenite at 510°C, and then partially transformed as desired to ~rlartensite by qnenching to - 196°C. Pole figures for the austenitic matrix and for the martensitic product were separately determined by an X-ray transmission method. The deforitration texture of' the warm-worked austenite is characlerized by (110)(225) components, and is thus closely similar to those produced in a brasses. The pole jigure of the martensite in partially transformed material agrees well with that which can be constructed by transfortnation of the {110)(225) orientations according to either the Kuvdjuniov- Sacks or the Nishi-yatuu relatiotship. Howeuer, an important result of this construction is that me-third of the predicted orientations are missing. A graphical analysis can then be used to show that in deformed austenite certain crystallographic variants of martensite (related to the most probable austenite slip systems) are suppressed, resulting in this preferred transformation. The evidence for preferred transformation is corroborated by the measured elastic anisotropy of warm-rolled and fully transformed H-11 steel. EXTENSIVE plastic deformation of a polycrystal-line aggregate in a manner that causes flow predominantly in one direction results in a preferred orientation of the constituent crystallites. The particular orientations that are produced depend upon the crystal structure and composition of the material, as well as upon the temperature, mode, and degree of deformation; in any case, the preferred crystallo-graphic orientations, or textures, are reflected in directionality of mechanical properties. Although such anisotropy may be exploited in certain specialized applications, it is more commonly diminished or eliminated by heat treatment lest it interfere undesirably in subsequent forming operations or in structural design. In the recently developed thermomechanical treatments that significantly enhance the strength of some steels,1,2 considerable deformation of the metastable austenite prior to the martensite transformation is essential to the strengthening process. If the austenite is textured by the deformation, and if the transformation to martensite proceeds according to one of the relationships established for transformation in annealed austenite, then it must be expected that the martensite will also possess a preferred orientation even though the multiplicity of martensite orientations possible in a given austen- ite crystal will tend to restore some degree of randomness. The existence of a residual anisotropy, both mechanical 3-6 and crystallographic,' has been substantiated. In the latter crystallographic investigation, preferred orientations were determined for the martensitic structure of an SAE 4340 steel rolled 72 pct as austenite at 833°C and then quenched. However, the choice of a composition that transformed almost completely to martensite during the quench to room temperature did not permit direct measurement of the prior austenitic texture. In fact, when the "ideal orientations'' associated with well-known fcc rolling textures were converted, alone or in combination, to martensite according to the Kur-djumov-Sachs (K-s)' or Nishiyama8 relations, the agreement obtained with the observed martensite texture was only fair at best. Recently a pertinent aspect of the austenite to martensite transformation was reported by Bokros and parker,10 who found that certain habit-plane variants of martensite were suppressed by tensile deformation of Fe-31.7 Ni single crystals prior to the necessary subzero cooling. It might be anticipated that the consequences of such preferred transformation are sustained during the formation of martensite in warm-worked austenite that has a well-developed deformation texture. The present investigation was undertaken first to establish more firmly the relation between preferred orientations in plastically deformed austenite and in the resulting martensite, and second to examine the textures for evidence of deformation-induced preferred transformation. EXPERIMENTAL PROCEDURES An alloy containing 0.3 pct C, 12 pct Cr, 6 pct Ni, and the balance iron, was selected because the mar-tensite-start temperature (M,) of about -100°C allowed convenient experimental manipulation of either austenite or martensite at room temperature. Furthermore, this composition can be readily deformed as metastable austenite at moderately elevated temperatures without intervention of appreciable isothermal or athermal decomposition products. The alloy was austenitized at 1150°C, aircooled to 510°C, rolled unidirectionally at this temperature to 93 pct reduction of cross-sectional area, and finally oil-quenched to room temperature. Partial transformation to martensite was accomplished by quenching to -196°C as needed. The rolled stock was reduced in thickness from 0.067 to 0.010 in. by etching in a solution of 5 pct HC1, 45 pct HNO3, and 50 pct water, and further thinned by careful mechanical polishing to maintain the two sides of the sheet parallel within 0.0003 in. After mechanical polishing to 0.005 in., electropolishing in 1:9 perchloric-acetic acid solution produced a final thickness of 0.002 in. The preferred orientations were determined from

Jan 1, 1968

By H. E. Cline, J. L. Walter

Grain boundary sliding and migration were studied in pure aluminum bicrystal and polycrystal samples with two-dimensional grain structure. Scratches, 50 P apart, were used for measurement of sliding and migration distanceso. Samples were deformed at constant rate at 315C and events recorded continuously on wrotion picture film. Electron micrograPhs of boundary-scratch intersections were obtained. Yield and flow stress values were measured. The sequence of sliding and migration events for a three-grain junction is described in detail. Sliding depended only on the resolved shear stress imparted to the boundary. Sliding was accowmodated by formation of shear zones in grains opposite triple points and adjacent to curved boundaries. These shear zones provided the driving force for grain boundary migration. Migration caused rumpling of the boundaries, decreasing the sliding rate. Sliding and migration generally began at the same time, occurred simultaneously and ended at the same time. In the bicrystal, sliding and migration rates were proportional. Initial sliding rules of 5 X joe cm per sec. were measured for the polycrystal and bicrystal samples. These sliding rates agree wilh the internal friction experirnents of K;. The observations seem consistent with a viscous boundary sliding nzechanism. GRAIN boundary sliding is the translation of one grain relative to its neighbor by a shear motion along their common boundary. Sliding is thought to be an important mode of deformation at elevated temperatures and at low strain rates such as prevail in creep,' and perhaps in the area of superplastic behavior.2"4 Although much work has been done to investigate grain boundary sliding, the effort has not led to the identification of a mehanism. KG showed that grain boundaries in aluminum exhibit a viscous nature under very small displacements of internal friction measrements. Various dislocation mechanisms have been proposed but are without conclusive experimental support. Attempts to relate sliding to 6's viscous boundaries have been unsuccessful in that measured rates of sliding are always several orders of magnitude lower than KG'S results would predict.= In bi crystals7and polycrystalsR of aluminum tested under constant load, the grain boundary sliding was found to be proportional to the total creep elongation which indicated that sliding might be controlled by deformation of the grains. Shear zones were observed to extend beyond grain boundaries at triple points to accommodate the sliding.8 Surface observations brought forth the opinion that sliding and migration occurred alternately, in sequence.' Measurements of sliding at the surface have been criticized because they might not be representative of the interior of the sample. Generally speaking, it seemed that much of the previous work and knowledge was based on observations made at relatively low magnification and examination of samples after deformation had been accomplished. Thus, it was the purpose of the present study to continuously record, at high magnification, the events occurring during the deformation of pure aluminum. Samples with two-dimensional grain structures were used to simplify interpretation of the results. The sliding and migration of small areas of many samples were continuously recorded by time-lapse motion pictures. Replicas of the surface were used to provide high-resolution electron micrographs. These observations, coupled with tmsile strength data, provide sufficient information to arrive at an understanding of the phenomenon. EXPERIMENTAL PROCEDURE An ingot of 99.999 pct A1 was rolled to sheet, 0.127-cm thick. Tensile specimens, with a gage length of 0.85 cm, were machined from the sheet. Bicrystal tensile specimens, of the same dimensions, were spark cut from a large bicrystal ingot. The grain boundary was oriented at 45 deg to the tensile axis. The surfaces of the tensile samples were ground flat on fine metallographic paper and were then electropolished in a solution of 75 parts absolute alcohol and 25 parts of perchloric acid. The solution was cooled in an ice-water bath. Using a weighted sewing needle suspended from a small pivot on a precision milling machine, a grid of fine scratches, 50 p apart, was scribed on one surface of the sample. The polycrystalline samples were then annealed in hydrogen for 15 min at 350" to 400°C to produce a two-dimensional grain structure of about 0.2-cm average grain diameter which would not undergo further growth at the test temperature, 315OC. Examination of both surfaces of the samples showed that the grain boundaries were perpendicular to the surface of the polycrystal and bicrystal samples. A hot-stage tensile machine was constructed for use with an optical microscope as shown in Fig. 1. The specimen is shown mounted in the grips. The grips ride in V-ways so that the sample can be mounted without damage. The rear grip is free to slide so that when the sample expands during heating it is not put under a compressive stress. When the grips and samples are at temperature, the rear grip is locked in place by two set-screws. The other grip is connected to a synchronous drive motor which, through a worm gear and a fine-threaded rod, deforms the

Jan 1, 1969

By H. S. Ten Eyck

Fertilizer normally is spoken of as having three main components: nitrogen, phosphorus and pot- ash. Certainly, however sulfur must also be considered a basic component of fertilizers, even though in many instances it does not end up as a part of the end product. In addition, with heavier cropping and the resultant drain of plant foods from the soil, we have now reached a point where the minor elements necessary for plant growth have become a major factor in the fertilizer industry.

Jan 7, 1967

By Robert C. Stephenson

LARGE deposits of titaniferous magnetite occur associated with anorthosite and gabbro in the Lake Sanford area, Essex County, New York. The ore, gabbro, and anorthosite show consanguineous relations. Anorthosite grades through gabbroic anorthosite into gabbro but is locally intruded by gabbro. Structural and petrographic evidence suggests that gabbro was differentiated from anorthosite by filter pressing. Field and laboratory study of ore occurrences indicates that an ore residuum concentrated in the gabbro through magmatic segregation by normal crystallization and flowage. Ore occurs as bands which grade into gabbro, and also as large masses which replace anorthosite. Ore in the gabbro is finer grained and richer in ilmenite than ore in anorthosite.

Jan 1, 1945