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By D. F. Stoneburner

The thermoelectric power and electrical conductivity of a series of liquid alloys of thallium were determined in order to study the relation of chemical bonding to semiconduction in liquids. The results indicate metallic behavior for the alloys of thallium with arsenic, antimony, and bismuth, while the sulfides, selenides, and tellurides indicate semiconduction. The results are compared with the Properties of the same alloys in the solid state. This work supports the observation that long-range order is not a necessary requirement for semiconduction. PREVIOUS work1,5 has shown that some sulfides and oxides behave as semiconductors in the liquid state. Although the band theory has been of great help in understanding the properties of solid semiconductors, its quantitative application to liquids is difficult. The very existence of liquid electronic semiconductors shows that ascribing the discrete structure of the energy spectrum to strict lattice periodicity, or long-range order, is not always satisfactory. Rather, the short-range order determines the structure of energy levels and the width of the forbidden gap and, consequently, the concentration of free holes and electrons. This is borne out by the analysis of data accumulated by Regel and coworkers.6 The similarity of electronic structure of liquid and solid phases of certain liquid metals was pointed out by Knight et a1.,7 who examined nuclear resonance in solid and liquid Li, Na, Rb, Cs, Mg, Al, Ga, Sn, and Bi. They found noticeable changes in the electronic structure upon melting only in the cases of bismuth and gallium. They concluded that "a liquid metal possesses a band structure which is very like that of the solid, provided the short-range structure is not altered during melting." In semiconductors in which the near-neighbor arrangement remains the same on fusion, the material would be expected to retain its semiconducting properties. The quantum theory of semiconductors, with its band structure of energy levels, is linked exclusively to long-range order. Furthermore, it has limited usefulness in predicting new semiconductors. Many sulfide8-12 have made comparisons of properties on the basis of crystal structure or the position in the periodic table, both methods involving the same factors as chemical bonding. Mooser and Pearson8"10 have pointed out that crystal structure depends on chemical bonding, and that this bonding is a property of the atoms themselves. As the periodic arrangement of the atoms offers an easy comparison of such factors as atomic weight and number of valence electrons it provides clues to expected similarities of bonding for various elements or groups of elements. This approach has led Mooser and Pearson to formulate their valence-bond theory of semiconduction, in which they define a semiconducting bond. These authors state that "semiconductivity is the result of the presence in a solid of predominantly covalent bonds. These lead, through the process of electron sharing, to completely filled s and p orbi-tals in the valence shells of all atoms of elemental semiconductors while in semiconducting compounds only one atom of any two bonded together need acquire closed s and p orbitals. The presence of empty 'metallic' orbitals in some atoms of a compound does not destroy the semiconductivity provided that these atoms are not bonded together; it may, however, give rise to pivoting resonance in

Jan 1, 1965

By George W. Orton

i\- number of investigations have established that tungsten monocarbide (WC) forms throughout a wide range of temperatures (800° to 2200°C), but the di-tungsten carbide (W2C) forms only at the high end of this temperature range.1"7 In addition the decomposition of WC into WzC and C at elevated temperatures has been observed.8"10

Jan 1, 1964

By J. T. Shapland

When externally mounted sliding-gate valves are used to control the flow of metal from ladles, none of the valve components are immersed in steel. In general, the refractories used to date in sliding-gate valves have been made of a high-alumina composition. Because these refractories replace the fireclay sleeves and clay-graphite heads used to construct conventional stopper rods, they represent a major change in the use of pouring-pit refractories, Changes in the well and lining of the ladle as a result of conversion to external flow control probably will not be as severe; however, the sliding-gate valve makes it possible to preheat to a higher temperature and to decrease the turnaround time, and materials more refractory than those currently employed, such as basic brick, might be used in these areas. Another area of pouring-pit refractories that has became quite important is the tundish used with continuous casters. The use of external flow-control devices on tundishes makes it possible to use the tundish for prolonged periods of time and makes the use of better refractories necessary. In this application, high-alumina and zirconia are finding acceptance.

Jan 1, 1972

By Pierre Hines

THESE notes are based on observations made while on a recent trip through the West, for the purpose of studying the practical operation of the ball-mill. The writer takes this opportunity to express his thanks for courtesies extended at the many plants visited as well as for the valuable data received. While there are several types of ball-mill on the market, particular attention will here be given to the diaphragm type, as the open-trunnion type, especially the conical mill, has been thoroughly discussed in the Transactions. There is a prevailing impression that the ball-mill is a recent development; however, ball-mills were used extensively in Montana and other western states for crushing ores for concentration as far back as 1898. Its present prominence is due in part to its recent successful application by one of the large copper companies. Without any reference to dry grinding, the first successful ball-mill for wet crushing, which is still in operation, was built 10 years ago.1 This mill, designed by Erminio Ferraris for crushing Sardinian ores for concentration, is of more than passing interest. It embodies the peripheral discharge with grates, large forged-steel balls, and the principal features of the modern ball-mill. The results approach present-clay practice, the chief differences being that the mechanical construction has been improved in the modern types.

Jan 2, 1918

By G. P. Pilling

The use of magnetic ore in the blast furnace is a subject of increasing importance. The end of the deposits of lake ore is in sight, although not imminent, and unless some new field is discovered, the use of magnetites will be an increasing factor in the iron production of the country. Enormous deposits of magnetic ore in the country that have been practically untouched contain ore of sufficient richness and purity to prolong materially our ore supply without extensive importation of foreign ores. Magnetic ores can be divided into three general classes: Fine un-sintered, or raw ore; raw lumpy ore; fine ore that has been sintered. Fine Unsintered Ore Typical analysis and screen test of this class of ore from the Adirondack region is as follows: Per Cent. SCREEN TeST pER Cent. Fe.................... 58.00 Remaining on 4 mesh........... 7.50 SiOz.................. 7.50 Through 4 on 8 mesh........ 13.75 Al,O,................. 1.60 8 on 10 meah........ 3.75 Baseg................. 2.77 10 on 20 mesh........ 22.50 P.................... 1.00 20 on 40 mesh........ 27.50 Mn................... 0.13 40 on 60 mesh........ 2.50 S..................... Trace 60 on 80 mesh........ 10.00 80 on 100 mesh........ 2.50 100 mesh........ 10.00 100.00

Jan 1, 1923

By G. P. Pilling

The use of magnetic ore in the blast furnace is a subject of increasing importance. The end of the deposits of lake ore is in sight, although not imminent, and unless some new field is discovered, the use of magnetites will be an increasing factor in the iron production of the country. Enormous deposits of magnetic ore in the country that have been practically untouched contain ore of sufficient richness and purity to prolong materially our ore supply without extensive importation of foreign ores. Magnetic ores can be divided into three general classes: Fine un-sintered, or raw ore; raw lumpy ore; fine ore that has been sintered. Fine Unsintered Ore Typical analysis and screen test of this class of ore from the Adirondack region is as follows: Per Cent. SCREEN TeST pER Cent. Fe.................... 58.00 Remaining on 4 mesh........... 7.50 SiOz.................. 7.50 Through 4 on 8 mesh........ 13.75 Al,O,................. 1.60 8 on 10 meah........ 3.75 Baseg................. 2.77 10 on 20 mesh........ 22.50 P.................... 1.00 20 on 40 mesh........ 27.50 Mn................... 0.13 40 on 60 mesh........ 2.50 S..................... Trace 60 on 80 mesh........ 10.00 80 on 100 mesh........ 2.50 100 mesh........ 10.00 100.00

Jan 1, 1923

By J. D. Pennock

The different samples of brick examined were Grecian magnesite, American magnesite; silica brick and coke-oven tiling made in Belgium and used in retort coke-ovens. The Grecian magnesite was furnished by a New Pork party. The American magnesite and the silica brick were furnished by a manufacturing company in Pittsburgh. From these brick were made cylindrical cores, '79 inches long and 15/8 inches in diameter. At one end of each was drilled a hole about 1/4-inch in diameter and 11/4 inches long, into which the thermometer was inserted during the experiment. Conductivity.—The apparatus used for determining the conductivity, as shown in Fig. 1, is a sheetriron drum, 18 inches in diameter and 8 inches high. In the center is a little combustion-chamber with walls of split fire-brick, 39 inches square and about 6 inches high. The fire-brick, however, pass through the drum to the table on which the drum stands. The cores are placed horizontally, half-way between the top and bottom of drum and on the line of diameters at right angles. In the four walls of the combustion-chamber are cut holes just large enough to allow the cores to pass through. The cores extend

Jan 1, 1897

By H. Hance James

SOME of the outstanding features of petroleum production in Illinois during 1923 were: (1) Sustained production from the older wells, due to cleaning and deepening; (2) good results from new drilling in a few localities; (3) large percentage of dry holes, many of which were ill advised tests, with a resulting high cost of the new production; (4) decrease in the number of productive wells in the state; (5) low average price of crude petroleum, a serious factor over the entire country. FIG. 1.-ANNUAL TOTALS OF ILLINOIS PRODUCTION. The total production of Illinois for 1923 was 8,710,000 bbl.,1 a decrease of 7.2 per cent. from that of 1922. Of this amount, it is estimated that about 8,500,000 bbl. were produced by old wells, many of which had been cleaned and deepened somewhat, and approximately 210,000 bbl. were obtained from the new wells drilled during the year. About 95 per cent. of the oil comes from the southeastern field in Clark, Crawford, and Lawrence Counties, where production is almost entirely from Pennsylvanian and Mississippian rocks. Extensions of the productive area were made in Clark, Wabash, Marion, and Jackson Counties. Some important gas development has been accomplished near Jacksonville, in Morgan County, and at Gillespie, in Macoupin County.

Jan 3, 1924

By Thomas C. Patton, Eric S. Cheney

L-D gold mine is 3 miles south of Wenatchee, central Washington. Recognition of locally mappable conglomerates, sandstones, and shales within the Paleocene (?) Swauk formation led to the discovery that the known epithermal gold mineraliza¬tion is limited to a previously unknown imbricate thrust zone of unknown displace¬ment cutting the open folds o f the area. Hypabyssal intrusions also are most nu¬merous along the trace of the thrust faults. Yakima basalt of Miocene age uncon¬formably overlies the Swauk formation, thrust faults, and the intrusions. The L-D mine is in a northwesterly trending imbricate fault block of nearly vertical strata. Microscopic native gold, electrum, and naumannite occur in quartz veins and as low¬grade disseminations in the well-silicified portions of arkosic sandstones. Fault gouge on the "footwall fissure" limits ore to the hanging-wall block of the fault. Epithermal mineralization and alteration are spatially related to the nearby intrusions. Right lateral north-south faults offset the ore a maximum of 300-400 ft along any one fault. From 1949 until January 1967, when the L-D mine closed, 1,036,572 dry tons of ore valued at $14,962,305 and averaging 0.396 oz Au per ton and 0.607 oz Ag per ton were mined. Recognition of the structural control of the mineralization and altera¬tion within the Swauk formation suggests several areas within and outside of the mine that warrant further exploration. For example, the high-angle faults, imbricate thrusts, and the intrusions of this area are on strike with similar features along the major Entiat fault zone 10 miles to the northwest. The L-D gold mine (previously called Squilchuck, Wenatchee, Golden King, Gold King, and Lovitt) is located in Squilchuck Canyon about three miles south of Wenatchee, Chelan County, Wash. (Fig. 1) on the eastern edge of the Cascade Mountains. The major stratigraphic unit in the area is the nonmarine early Tertiary Swauk formation, which is predominantly com¬posed of arkosic sandstone. The lack of laterally per¬sistent units and the paucity of outcrops heretofore have precluded all but the grossest subdivision of the Swauk.' As a result, the true significance of the open folds in the Wenatchee area was not recognized, and although the geology within the mine was known, the structural setting of the mine was virtually unknown. During the present investigation, several locally map¬pable units were discovered within the Swauk which, in conjunction with mine maps, indicate an imbricate thrust zone. The epithermal gold mineralization, most of the hypabyssal intrusions, and the zones of hydrother¬mal alteration are located within or near this thrust zone. The purpose of this paper is to: (1) to describe this structural setting, rather than the detailed mine geology already presented by Lovitt and Skerl,2 and (2) to sug¬gest that from an exploration standpoint, this struc¬tural setting may be repeated in areas inside and outside of the mine area. Stratigraphy and Structure of the Swauk Formation General: The Swauk formation contains three distinct lithologies. Typical Swauk sandstone is gray on fresh surfaces, poorly sorted, weathers tan, and is cross¬bedded; it consists of 40-60% quartz, 20-40% feldspar, and up to 10% muscovite and biotite 9 The typical shale is gray to dark brown, very soft, and interbedded with silty sandstones; sharp contacts exist between the

Jan 1, 1972

By H. Eklund, R. T. Hukki

This article presents a simple arithmetic derivation for the relationship between sharpness of classification and circulating load, as well as world-wide industrial data which are compatible with the derived equation. It is shown that the sharpness of classification decreases with increasing circulating load. Based on the evidence available a comparison is presented between the performance of the present-day hydraulic classifiers. In a continuously operated closed circuit grinding system the tonnage and the fineness of the components may be indicated as follows: Eq. 8 expresses the relationship between sharpness of classification and circulating load in closed grinding circuits. If CL = 0, E = 100% according to the definition used. This, however, is a purely theoretical case because any apparatus to be called a classifier must produce the conventional two products. Furthermore, if CL = m, E =0%. In order to visualize the meaning of Eq. 8, the effect of factors d (fineness or percentage of under-size of classifier overflow at size x) and b (fineness or percentage of undersize of classifier sands at size x) should be studied. By the most rigid standard, factor d should be given the value of 100%. By so doing the size of classification is defined as that screen size x through which 100% of the classifier

Jan 1, 1965

F. C. LANGENBERGW.*at 8ertoivn,M ass. (written cliscussiont).-I am inclined to the view that the change in physical properties encountered in the material with which the authors are working is due to the relief of internal strains. The statement, on page 1.098 of their paper, calling attention to the fact that this phenomenon disappeared when the material was rolled into 1 7/8 -in. square billets is of particular interest. It is certain that the internal strains set lip by cooling in a small billet of this size would be much less than those produced in a billet having a larger cross-section cooling under the same conditions. The statement that the physical properties of a given test bar were materially changed by standing has been brought to my attention in connection with the testing of gun forgings. I have made a number of observations on forgings produced at Watertown Arsenal to ascertain whether any change in ductility was produced by the aging of the test specimens. The results were always negative, but this can be explained by the fact that ii gun forging is generally a forging that has been quenched and subsequently drawn at a relatively high temperature.

Jan 10, 1919

By R. K. Adams

The availability of digital computers costing less than $15, 000 makes them economically attractive as versatile research and experiment tools. Several such installations at Oak Ridge National Laboratory have shown that improvements in research productivity and experimental control accuracy can result from the proper application of a small digital computer. However, careful attention must be paid to several potentially expensive problems in 1) interfacing the experiment to the computer and 2) programming the computer. Two specific applications of very small computers to metallurgical testing and research are described. One is a system for data acquisition and precise temperature control associated with a thermocouple testing program, and the other is a system for pulse calorimetry determination of the specific heat of metals over wide temperature ranges and in the neighborhood of metallurgical transformations. The data acquisition system which uses a PDP-8/S computer monitors signals from up to 264 low-level thermocouple signals at two scanning speeds: 10 readings per second for long-term drift data, and 500 readings per second for transient data. The pulse calorimetry system which uses a PDP-8 computer accepts up to 6 signals of 0- to 10-v range and because of a larger analysis program, uses a bulk memory (magnetic disc) in addition to core memory.

Jan 1, 1969

By C. H. Li, R. J. Stokes

This paper compares the fracture behavior of tungsten rods in three conditions: recrystallized. recovered, and wrought. Notched specimens suhjected to a 50 in.-lb impact load showed ductile-brittle transitions at 700, 4.90°, and 440°C, respectinely. The recrystallized material had an equiaxed pain structure and jracbred by simple cleavage from a grain boundary source at all temperatures up to 700°C. The wrought and recovered material had an elongated fibrous structure and at low temperatures fractured by cleavage originating from the notch. As the transition temperature was approached cleavage was preceeded by more and more intergvanular splitting which deflected the crack front into planes parallel to the tensile axis. The enhanced toughness of wrought and recovered tungsten was attributed both to its inability to initiate cleavage because no pain boundaries were suitably oriented perpendicular to the tensile stress and to its inability to maintain cleavage because of intergranular splitting ahead of the crack. It has been appreciated for a long time in a qualitative manner that the room-temperature brittleness of fully recrystallized tungsten may be alleviated by working the material at relatively low temperatures.' More recently this difference in mechanical behavior between wrought and recrystallized tungsten has been examined quantitatively by measurement of the tensile properties as a function of temperature. In these experiments brittleness has been expressed in terms of ductility or reduction in cross-sectional area upon tensile fracture or in terms of the bend radius before fracture under bending.' This work has shown the existence of a fairly sharp transition from brittle to ductile behavior with an increase in temperature. The ductile-brittle transition temperature for recrystallized material is approximately 200°C higher than for wrought material. An increase in strain rate, small additions of impurity,' or an increase in grain size4 shift the respective transition temperatures to higher values, but the difference between them remains approximately the same at 200°C. A number of explanations for this embrittlement by recrystallization have been given. It has been blamed either on the concentration of impurity at the grain boundaries, the increase in grain size, or the change in texture which occurs upon recrystallization. The present paper examines the effect of different heat treatments on the notch-impact behavior of commercial powder-metallurgy tungsten rods. The change in the ductile-brittle transition temperature for this method of loading and the fracture mode has been related to the different mi-crostructures produced by heat treatment. EXPERIMENTAL PROCEDURE Commercial swaged powder-metallurgy tungsten rods 1-3/8 in. in length and 1/8 in. in diameter were machined to introduce a sharp V notch 0.030 in. deep. To change the microstructure from that of the as-received wrought material some of the specimens were subjected to an anneal in nitrogen either at 1300° or 1400°C for 8 hr or at 1600° or 2000°C for 1/2 hr. The notched rods were then placed in a miniature Charpy-type impact machine and struck at their midpoint (opposite the notch) with a hammer designed to deliver 50 in.-lbs of energy. The strain rate at the base of the notch was estimated to be approximately 100 sec-1 at the instant of impact. The specimens were heated in situ to the desired impact temperature. The microstructures produced by the various anneals were studied by both X-ray diffraction and metallographic techniques. Fig. 1 reproduces the microstructures observed metallographically following a 10-sec electroetch in a 10 pct KOH solution. Fig. l(a) shows the elongated fibrous grain structure of the as-received material. Following the anneal at 1300" or 1400°C the grain structure was still elongated as shown in Fig. l(b) but the etch pits delineated dense polygonized dislocation arrays within many of the grains. Occasionally a relatively dislocation-free recrystallized grain was found growing into the matrix. The anneals at 1600° and 2000°C resulted in complete recrystallization and some grain growth. The grains produced at 1600°C were still slightly elongated as shown in Fig. l(c) whereas the anneal at 2000°C produced equiaxed grains. The changes in grain size produced the expected changes in the X-ray back-reflection patterns; there was no indication either in the as-received material or the annealed material of any preferred orientation. RESULTS a) Impact Behavior. Fig. 2 reproduces the ductile-brittle transition curves measured in the manner described in the previous section. It can be seen that under these testing conditions the as-received

Jan 1, 1964

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'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.' 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 A. H. Larson, L. G. Twidwell

The influence which Au, Ag, Sb, Bi, Sn, and Cu have, both individually and collectively, on the activity coefficient of sulfur in liquid lead at 600"C zuas studied by circulating a H2S-Hz gas wlixture over a specific lead alloy until equilibrium was attained. Subsequently, the H2S concentration in the equilibrium gas mixture and sulfur concentration in the condensed phase were deterruined. The elements gold, silver, and antinzony (above 8 at. pct) increased the activity coefficient of sulfur. Bismuth had no apparent effect. Tin (above 3 at. pct) and copper decreased the coefficient. The influence of an individual element, i, on sulfur is best reported as the interaction parameter, riS, which is defined as The values o these first-order interaction zus are: ESzu = —55.0. These interaction parameters are used to predict the activity coefficient of sulfur in six fouv-component alloys and one seven-component alloy. Comparisons are made with direct experimental determinations. INTERACTIONS in dilute solution have been studied by many investigators. Most of the experimental work has been confined to solute-solvent interactions in simple binary systems and solute-solute interactions in ternary systems. Dealy and pehlke"~ have summarized the available literature on activity coefficients at infinite dilution in nonferrous binary alloys and have calculated from published data the values for interaction parameters in dilute nonferrous alloys. Interaction parameters are a convenient means of summarizing the effect of one solute species on another in a given solvent. Only a few investigators have studied interactions of the nonmetallic element sulfur in a metallic solvent. They are as follows: Rosenqvist,~ sulfur in silver; Rosenqvist and Cox,4 sulfur in steel; chipman, sulfur in alloy steels; Alcock and Richardson,% ulfur in copper alloys; Cheng and Alcock,' sulfur in iron, cobalt, and nickel; Cheng and ~lcock,' sulfur in lead and tin. The only reported work on the Pb-S system in the dilute-solution region is that of Cheng and Alcock.' Their investigation involved a study of the solubility of sulfur in liquid lead over the temperature range 500" to 680°C. The results may be summarized by the following relationship: S (dissolved in lead) + Pb(1) = PbS(s) log at. %S = -3388/T + 3.511 Experimentally, it was found that Henry's law was valid up to the solubility limit of sulfur in lead, i.e., at 600°C up to 0.43 pct. Their investigation did not include the study of sulfur in lead alloys. More accurate calculations could be made in smelting and refining systems if activity coefficients of solute species could be accurately predicted in complex solutions. One of the objectives of this study was to compare the experimental data with the values calculated from the equations derived from models for dilute solutions proposed by wagner9 and Alcock and Richardson. A temperature of 600°C was chosen as the experimental temperature to attain reasonable reaction rates and to minimize volatilization of the condensed phase. EXPERIMENTAL Materials. The Pb, Au, Ag, Sb, Bi, Sn, and Cu used for preparation of the alloys were American Smelting and Refining Co. research-grade materials. All were 99.999+ pct purity except the antimony and tin which were 99.99+ pct. The initial alloys prepared for this study consisted of twenty-one binary alloys, eleven ternary alloys, and one six-component alloy. The constituent elements were mixed for each desired alloy and were placed in a crucible machined from spectrographically pure graphite. The crucible was placed in a vycor tube which was evacuated with a vacuum pump and gettered by titanium sponge at 800°C for 8 to 12 hr. After the gettering was completed, the chamber containing the titanium was sealed and removed. The remaining sample chamber was placed in a tube furnace at 800°C for 2 hr and quenched in cold water. The final operation consisted of homogenization of the alloy for 1 to 2 weeks at a temperature just below the solidus for the individual system. The resulting master alloys were sectioned into small pieces and a random choice made for individual equilibrations. Cobalt sulfide (Cogs8) used to control the gas atmosphere in the circulation system was prepared by passing dried HzS for 24 hr over a Co-S mixture heated to 700°C in a tube furnace. This material was then mixed with cobalt metal to give a two-phase mixture which, when heated in hydrogen to a particular temperature, produced a desired H2S/H2 gas atmosphere in the circulation system. A Cu2S-Cu mixture also used in this study was prepared in a comparable manner. Apparatus for Equilibrium Measurements. The experimental technique of this study required apparatus

Jan 1, 1967

LIST OF THE MEETINGS OF THE INSTITUTE AND THEIR LOCALITIES FROM ITS ORGANIZATION Transactions Number Place Date Vol Page 1 Wilkes-Barre, Pa May, ?71 1 3 2 Bethlehem, Pa August, ?71 1 10 3 Troy, N Y November, ?71 1 13 4 Philadelphia, Pa February, ?72 1 17 5 New York, N Y May, ?72 1 20 6 Pittsburg, Pa October, ?72 1 25 7 Boston, Mass February, ?73 1 28 8 Philadelphia, Pa May, ?73 2 3 9 Easton, Pa October, ?73 2 7 10 New York, N Y February, ?74 211 11 St Louis, Mo May, ?74 3 3 12 Hazleton, Pa October, ?74 3 8 13 New Haven, Conn February, ?75 3 15 14 Dover, N J May, ?75 4 3 15 Cleveland, 0 October, ?75 4 9 16 Washington, D C February, ?76 4 18 17 Philadelphia, Pat June, ?76, 5 3 18 Philadelphia, Pa October, ?76 5 9 19 New York, N Y February, ?77 5 27 20 Wilkes-Barre, Pa May, ?77 6 3 21 Amenia, N Y October, ?77 6 10 22 Philadelphia, Pa. May, ?78 6 18 23 Chattanooga, Tenn May ?78 7 3 24 Lake George, N.Y. Oct. ?78 7

Jan 1, 1923

LIST OF THE MEETINGS OF THE INSTITUTE AND THEIR LOCALITIES FROM ITS ORGANIZATION Transactions Number Place Date Vol Page 1 Wilkes-Barre, Pa May, ?71 1 3 2 Bethlehem, Pa August, ?71 1 10 3 Troy, N Y November, ?71 1 13 4 Philadelphia, Pa February, ?72 1 17 5 New York, N Y May, ?72 1 20 6 Pittsburg, Pa October, ?72 1 25 7 Boston, Mass February, ?73 1 28 8 Philadelphia, Pa May, ?73 2 3 9 Easton, Pa October, ?73 2 7 10 New York, N Y February, ?74 211 11 St Louis, Mo May, ?74 3 3 12 Hazleton, Pa October, ?74 3 8 13 New Haven, Conn February, ?75 3 15 14 Dover, N J May, ?75 4 3 15 Cleveland, 0 October, ?75 4 9 16 Washington, D C February, ?76 4 18 17 Philadelphia, Pat June, ?76, 5 3 18 Philadelphia, Pa October, ?76 5 9 19 New York, N Y February, ?77 5 27 20 Wilkes-Barre, Pa May, ?77 6 3 21 Amenia, N Y October, ?77 6 10 22 Philadelphia, Pa. May, ?78 6 18 23 Chattanooga, Tenn May ?78 7 3 24 Lake George, N.Y. Oct. ?78 7 25 Baltimore, Md. Feb. ?79 7

Jan 1, 1923

By J. W. Clark, C. T. Sims

Wrought chromium-base alloys containing yttrium, cubic monocarbides of the Ti(Zr)C type, and similay alloys containing manganese and rhenium have been melted and fabricated. Strength has been studied by hot hardness and elevated-temperature tensile and rupture measurements, low-temperature ductility by tensile testing, and surface stability by oxidation testing. In additiod, studies have been conducted of the carbide stability, and of aging behavior. The carbide dispersion generates effective elevated-temperature strength, which is further enhanced hv strain-induced precipitation. The dispersion exhibits classical dissolution and aging response. The ductile-to-brittle transition temperature of these alloys is above room temperature. The alloys reported show fairly good oxidation resistance, but nitrogen contamination can cause fortnation of a hard Cr2N layer under the oxide scale. Manganese does not appear to be a promising alloying element in chromium. In the years 1945 to 1950, the metal chromium was considered as a possible base for alloy systems due to its considerably higher melting point than superalloys, its low density, its high thermal conductivity, and its apparent capacity for strengthening. However, this interest in chromium was short-lived. It was found difficult to melt and cast, to be exceptionally sensitive to the effect of minor imperfections, to have a lack of ductility at both room and elevated temperatures, and to be subject to a deleterious effect of alloying elements upon the ductile-to-brittle transition temperature.' Since then, chromium, as a practical alloy base, has remained virtually unstudied. Further, purposeful ignoring of chromium has been promoted by statements that its bcc structure would not allow it to be strengthened to useful values, when compared to the "austenitic" alloys.2 Recently, a new look has been taken at chromium-base alloy systems. Study of the literature will show that chromium, providing some of its disadvantages could be eliminated or minimized, actually has a rather attractive potential as an alloy-system base. Analysis of rather scattered data suggests that chromium is quite capable of being strengthened to high levels. Also, significant strengthening of its two sister elements in Group VI-A, molybdenum and tungsten, has been demonstrated in a number of commercial and exploratory alloys. Chromium should be similar. Since chromium does not readily form a volatile oxide like tungsten or molybdenum, it offers a much higher probability of giving birth to alloy systems with useful oxidation resistance. Concerns about possible high elemental vapor pressure have been mitigated by recent data.3 In addition, the physical properties exhibited by chromium are attractive for application as a high-temperature structural material. For instance, its thermal conductivity varies from 49 to 36 Btu-ft/hr-sq ft-°F over its range of usefulness (which is two to four times higher than most superalloys), its density is about 7.2 g per cc (20 pct less than most nickel-base alloys), its coefficient of thermal expansion varies from 4 to 8 x 10-6 per OF, and it has a relatively high modulus of elasticity, approximately 42 x 10' psi.4 Alloying studies on a chromium base in the past have usually encompassed rather sweeping solid-solution alloy additions for strengthening. This is not consistent with contemporary alloying practice in Group VI-A. For instance, molybdenum, also in Group VI-A, is primarily alloyed for strength improvement by use of heat-treatable carbide dispersions.5 Chromium and molybdenum are similar in their chemical activity and other properties. Thus, strengthening of chromium by carbide dispersions was studied. Chromium-base alloys are plagued with room-temperature brittleness, although high-purity unal-loyed chromium can be made ductile.4,8 Use of yttrium as a scavenger has done much to improve ductility and resistance to nitrogen embrittlement in chromium systems,7 so it was utilized in this program. It has also recently been found8 that small rhenium additions (1 to 5 pct) create improvement in the ductility of Type 218 tungsten wire. This is apparently related to the remarkable effect of rhenium additions near its terminal solid solubility in all Group VI-A metals.9'10 Investigation to establish if dilute concentrations of rhenium would also be effective in chromium appeared to be logical for this program. Since rhenium is too expensive to be practical in alloys for application as structural components, ductility improvements through solid-solution alloying were also sought by substitution of manganese for rhenium; manganese, like rhenium, exists in Group VII of the periodic system. The optimum amount of carbide dispersion for chromium-base alloys was obtained by analogy with molybdenum. Strengthening in molybdenum is achieved by use of Ti-Zr carbide dispersions. A

Jan 1, 1964

By E. J. Rapperport, E. D. Levine

The boundaries of the (a +ß) field in the Al-Li system were determined between 150°and 550°C utilizing quantitative metallography and lattice-parameter measurements. The solubility of lithium in aluminum decreases from 12.0at. pct Li at 550°C to 5.5 at. pct Li at 150°C. P Al-Li is saturated with aluminum at 45.8 at. pct Li and has this boundary value constant over the temperature range 150°to 550°C. THE solid solubility of lithium in aluminum has been determined by several investigators, 1-6 but, as shown in Fig. 1, there is little agreement among the various determinations. The earliest investiga-tions'-' are suspect because of the use of impure materials. Although high-purity materials were employed in more recent work,4'5 the experimental techniques may have led to contamination of the specimens. Probably the best work has been that of Costas and Marshall,6 who obtained close agreement between results obtained by two independent phase-boundary techniques: electrical resistivity and mi-crohardness. No detailed studies of the solubility of aluminum in the bcc ß phase, Al-Li, have been reported. Cursory investigations1,2,6 have indicated only that the (a+ß) -p boundary lies between 40 and 50 at. pct Li and is relatively independent of temperature. The present work was undertaken in order to provide an independent check on Costas and Marshall's determination of the solubility of lithium in aluminum, to extend knowledge of this solubility limit to temperatures below 225°C, and to make an accurate determination of the solubility of aluminum in Al-Li. EXPEFUMENTAL Alloy Preparation. In view of the difficulties encountered in previous investigations of the A1-Li system, close attention was paid to the use of methods of alloy preparation and treatment that would minimize contamination. Aluminum sheet (99.99 + pct Al) was vacuum-induction melted in a beryllia crucible to remove hydrogen. Lithium (99.9 pct Li) was charged with pre-melted aluminum into a beryllia crucible, in a helium-filled drybox. The crucible was sealed in a Vycor tube and transferred from the drybox to an induction furnace. Melting of alloys was performed by induction heating in a helium atmosphere. Solidification was accomplished by means of a suction apparatus, shown in Fig. 2, in which the alloy was forced by changes of pressure into a 3/16-in. inside diam closed-end beryllia tube. This technique produced rapid solidification of a small portion of the melt, resulting in alloys with a high degree of homogeneity. Typical lithium distributions are presented in Table I. Transverse sections 1/8 in. long were cut from the alloy rods, and each section was split in half longitudinally. One half of each section was analyzed for lithium, and the opposing halves were employed for phase-boundary determinations. Lithium contents were determined by flame photometry with an accuracy of 1 pct of the amount of lithium present. Thermal Treatments. Homogenization and equilibration heat treatments were performed in electrical-resistance furnaces with temperatures controlled to ± 2OC. Calibrated chromel-alumel thermocouples were employed to measure temperature. Homogenization was performed in helium-filled l?yrex tubes for 1 hr at 565°C. The encapsulated specimens were then transferred directly to furnaces maintained at lower temperatures for equilibration. Equilibration times were 2 hr at 550°C, 8 hr at 450°C, 27 hr at 350°c, 90 hr at 250°c, and 285 hr at 150"~. These times were chosen on the basis of conditions employed by previous investigators. Alloys were quenched from the equilibration temperatures by breaking the capsules into a silicone oil bath. By performing all possible operations either in sealed capsules or in a helium-filled drybox, the specimens were given minimum exposure to the atmosphere. Quantitative Metallography. Metallography of Al-Li alloys is difficult because of the atmospheric reactivity of the ß phase. It was found possible, however, to prepare surfaces of good metallographic quality by preventing contact with moisture during preparation. Grinding through 4/0 paper was performed in the drybox. The specimens were then transferred under kerosene to the polishing wheel. Three polishing stages were employed: 25-p alundum with kerosene lubricant on billiard cloth, 1-µ diamond paste on Microcloth, and 1/4-p diamond paste on Microcloth. Between stages the samples were cleaned by rinsing in trichloroethylene and buffing

Jan 1, 1963

By B. B. L. Seth, H. U. Ross

A generalized rate equation for the reduction of iron oxide was derived from which two particular equations were obtained: one for rate controlled by the transportation of gas, the other for rate controlled by the phase-boundary reaction. Pellets of pure ferric oxide having diameters of 8.5 to 17.5 mm and a density of 4.8 g per cm3 were prepared and reduced by hydrogen at 750° to 900°C. From the analysis of data obtairzed, it was observed that neither the phase-houndarv reaction nor the transportation of gas controlled entirely the rate of redziction. Rather, the mechanism of reduction can he divided into three stages. In the beginning, the process seems to depend predominantly on the surJrce reaction, hut after a layer of iron is formed the diffusion of gas becomes the controlling factor. Towards the end, however, the rate falls sharply due to a decrease in porosity. The times predicted by the generalized equation for a certain degree of reduction showed an excellent agreement with those obtained experinmentally for pellets of varying sizes. WIDE interest in iron oxide reduction has resulted in many valuable studies pertaining to thermody-namical properties, equilibrium diagrams, and chemical kinetics. Although the thermodynamical properties and equilibrium diagrams are now known with a fair degree of accuracy, the mechanism and rate-controlling step in the reduction of iron oxides presents a problem to research workers which is still unsolved. This is because the field of chemical kinetics is so highly complex. Besides the chemical reaction between oxide and reducing gas, several other processes are occurring simultaneously such as solid-state diffusion of iron through intermediate oxides (FeO and Fe3O4), the diffusion of reducing gas inwards and of product gas outwards, and the sintering of iron if reduction is carried out above the sintering temperature of iron. Furthermore, there is a large number of variables, including the nature and flow rate of the reducing gas, the chemical composition and physical properties of the ore, the temperature of reaction, particle size, and so forth, all of which can affect both the mechanism and the kinetics of reduction. Despite the controversy and diversity of opinion about the mechanism of iron oxide reduction, three main schools of thought have emerged. According to the first, the rate is controlled by the diffusion of gas through the boundary layer of stagnant gas; the second claims that the rate is proportional to the area of the metal-oxide interface, while the third believes the transportation of reducing gas from the main stream to the metal-oxide interface and of product gas from the metal-oxide interface to the main stream to be the rate-controlling step. 1) The boundary-layer theory is true mainly for packed beds where the flow of gas through the bed is important. For a single particle, the boundary layer may be prevented from being the rate-controlling step if a gas flow rate of reducing gas above the critical flow rate is used. 2) Several workers have reported a linear advance of the Fe/FeO interface which provides excellent support for the belief that reduction is controlled by the surface area. McKewanl has given formal shape to this concept with mathematical derivation and has shown it to be valid for reduction of several iron ores, hematite, and magnetite, both by H2 and H2, H2O, N2 mixtures. Some other investigators, however, do not find this theory to be entirely valid. Deviations have been observed2 and further confirmedS3 Hansen4 also agrees that deviations do occur, at least in the latter stages of reduction, while from the data of several investigators summarized by Themelis and Gauvin,5 it is clear that the theory is not always applicable and further that, when it is applicable, it does not hold in the final stages of reduction. 3) Among those who claim the transportation of gas to be the rate-controlling step are Udy and Lorig,6 Bogdandy and Janke,7 and Kawasaki el a1.8 The validity of the theory has also been acknowledged indirectly by other research workers who show that the sintering and recrystallization of iron cause a decrease in reduction rate, for it is only if the transportation of gas is important that this sintering has any bearing. However, the theory has been rejected by some because they have failed to obtain

Jan 1, 1965