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By W. M. Wojcik, R. F. Kowal

Oxygen and sulfur distributions in commercial, 5-ton ingots of killed, medium carbon steel are described. Oxygen distribution is found to vary with deoxidation practice. Irregular distribution of oxygen within ingots makes necessary special precautions in sampling of rolled products for analysis of oxygen. Oxygen distribution is discussed in terms of recently published solidification concepts which had been successfully applied to simpler cases of segregation. These concepts have been found inadequate to explain observed oxygen distributions. Convective movements of the liquid metal, as determined by tracer elements, are shown to be capable of accounting for the observed distributions of oxygen. IN an effort to explore the origin of surface and subsurface imperfections in pierced steel products, a study of oxygen and sulfur segregation was made on ingots cast in open-top and hot-top molds. The results of our previous investigations1"3 have indicated the importance of the location and amount of oxide inclusions in an ingot. Inclusions close to the surface of the ingot have been found to contribute greatly to the formation of imperfections in the surface of finished products. This study of the effects of deoxidation and casting practice on segregation and the resulting oxygen distribution in ingots was initiated to determine the parameters controlling the location of inclusions in an ingot. Segregation of solute elements during solidification of low-melting binary alloys has been studied in the past.1, 5 Formation and growth of inclusions in iron melts have been studied under specific conditions."- In spite of these and other recent studies,10-12 segregation during solidification of commercial, killed steel ingots is not well understood. Consideration of solidification rates, of segregation during solidification of the chill, dendritic, and central zones, and of material balances for the segregated elements has indicated that a simplified theoretical solidification model is not adequate. However, the observed high oxygen contents in localized volumes of the dendritic zone can be rationalized if additional effects of convection currents in the ingots, precipitation, and rapid growth of new phases are considered. EXPERIMENTAL PROCEDURE Steelmaking and Processing. A group of nine killed. medium carbon steel heats having compositions listed in Table I have been studied. The deoxidation and mold practices used were varied to give a wide range of steel oxygen contents. The amounts of aluminum added to the ladle and the ingot casting practices (hot top and open top) were the main variables. The steel was made by a duplex practice in 160-ton tilting basic open-hearth furnaces. All nine heats were top-cast into 24 by 24 in. big end down, fluted molds, to a height between 60 and 76 in., using both open tops and exothermic hot tops. The deoxidation practice and the tapping and teeming details for each heat and ingot studied are given in Tables II and III, respectively. Hot-top practice is indicated by the letter H following the heat designation. Furnace and ladle temperatures were measured by standard disposable-tip, Pt/10 pet PtRh thermocouples. Teeming-stream temperatures were obtained as described by Samways et al.,13 by immersing a Pt/10 pet PtRh thermocouple, covered by a silica sheath, into the teeming stream under the nozzle. The output of this thermocouple was recorded with Leeds & Northrup Speedomax potentiometer. Calibration of the latter thermocouples was based on the freezing point of a pure iron/oxygen alloy (2795°F). The accumulated errors of measurements were within ±10°F. The thermocouple measurements were supplemented in this investigation by continuous recording of a ratioing, two-color pyrometer (Shawmeter), protected from smoke by a blast of clean air within the sighting tube, and calibrated to read with better than ±10°F accuracy. Following teeming of three heats, P, R, and T, tracer elements were added to the steel in the molds to obtain a record of the progress of solidification. As soon as the teeming stream was shut off, a 0.010-in.-thick steel can containing a mixture of crushed standard ferro-titanium and ferro-vanadium (0.05 pet of each alloy element) was plunged into the middle of the steel pool to a depth of 6 in. In about 30 sec no indication of the can or its contents remained. The surface of the open-top ingots solidified in 20 to 30 sec. A study of liquid metal movement and the precipitation of oxides was facilitated materially by use of the tracer technique as titanium has a low distribution coefficient between solid and liquid steel while vanadium has a high distribution coefficient.

Jan 1, 1965

By A. U. Seybolt

The solubility limit of oxygen in columbium has been determined in the range between 775' and 1100°C by means of lattice parameter measurements and microscopic examination. The solubility is a function of temperature and varies, in the range given above, from 0.25 to 1.0 pct O, respectively. BECAUSE of the marked deleterious effect of oxygen upon the mechanical properties of some of the transition metals, it is desirable to know something about the solubility of oxygen in these metals. The brittleness caused by oxygen in solution is particularly marked in the case of the group VA elements, vanadium, columbium, and tantalum. The solubility of oxygen in vanadium has already been reported in an earlier paper,' and Wasilewski2 has given a value (0.9 wt pct) for the solid solubility of oxygen in tantalum at 1050°C. Brauer3 in 1941 investigated the Cb-0 system up to Cb2O5, but made no real effort to investigate the extent of oxygen solubility in the metal. He made the observation, however, that this solubility must be less than 4.76 atom pct (0.86 wt pct) oxygen. This estimate was made from X-ray diffraction results on the alloys CbO, CbO, and CbO; all alloys consisted of the terminal (Cb) solid solution plus CbO, but the last alloy containing 4.76 atom pct 0 showed only three very weak CbO lines. It is surprising that Brauer, by examining only three alloys, arrived at an estimate of the solubility which agrees very well with the results to be reported herein. Experimental Procedure A columbium strip obtained from Fansteel Metallurgical Products was cut into strips, 0.020x1/2x2 in. Two holes, about 3/16 in. in diameter, were made near the ends of the strips in order to hold them against a flat steel block for mounting in a General Electric X-ray spectrometer for lattice parameter measurements. The same holes were used to hang the specimens inside a fused silica vacuum furnace tube which was part of a Sieverts' gas absorption apparatus. The apparatus and method of adding oxygen gas has been previously described.1 According to the supplier, the columbium obtained had the analysis given in Table I. After degreasing the samples, approximately 0.001 in. was etched from each side of the samples in order to remove possible surface impurities from the last rolling operation. For this purpose the following cold acid pickle was found satisfactory: 8 parts HNO3, 2 parts H2O2 and 1 part HF. Various Cb-O compositions were obtained up to 0.75 wt pct O by the gas absorption and diffusion technique. After the sample had absorbed all the oxygen gas added at 1000°C, an additional 24 hr was allowed for homogenization. This treatment appeared to be adequate, as shown by the linearity of the lattice parameter-composition plot. More concentrated alloys were prepared by arc melting mixtures of Cb and Cb2O5 since it was very time-consuming to make Cb-0 alloys in the neighborhood of 1 pct O, or over, by the diffusion method. When the flat strip specimens were used, they were ready for the X-ray spectrometer after cooling from the Sieverts' apparatus. The cooling rate obtained by merely allowing the hot fused silica furnace tube to radiate to the atmosphere (when the furnace was lowered) was sufficiently fast to keep the dissolved oxygen in solution. Arc-melted alloys were reduced to —200 mesh powder in a diamond mortar, wrapped in tantalum foil, sealed off in evacuated fused silica tubes, and then heat treated as indicated in Table 11. The fused silica tubes were quickly immersed in cold water without breaking the tubes after the heat treatments. The tantalum foil prevented reaction between the fused silica and the sample; there was no reaction between the powdered samples and the foil at 1000°C, but some trouble was experienced at 1100°C. At this temperature level a reaction between the sample and the foil was sometimes observed, which resulted in erroneous parameter values. Experimental Results Hardness Tests: Since most of the X-ray samples were in the form of flat strip, it was convenient to obtain Vickers hardness numbers as a function of oxygen content. Compared to the V-O case,' oxygen hardens columbium much more slowly, presumably because of the larger octahedral volume in colum-bium (about 12.0 compared to 9.3Å3 in vanadium), hence, requiring less lattice strain for solution. The plot of VHN vs wt pct O is shown in Fig. 1.

Jan 1, 1955

By E. P. Mathewson

THE experiments described in this paper were made at the Washoe Reduction Works, Anaconda, Mont., for the purpose of determining the relative speed of elimination of the iron, sulphur and arsenic during the process of bessemerizing copper-mattes. The samples were taken from a horizontal "barrel" converter, 8 ft. in diameter and 12 ft. 6 in. long, having an average charge of 9 tons of matte, and blown with a 16-1b. air-pressure. All samples were taken with the blast on, turning the converter from its normal blowing-position to nearly verti¬cal, so that a conical mold, with a long handle attached to a horizontal rod, could be introduced from a platform above the converter into the mouth of the converter and a sample taken. The difficulties of taking a sample with the blast on are appar¬ent, and the irregularities of the lines in Figs. 1, 2 and 3 can be readily accounted for by the amount of slag in the samples. On the whole, the plotting of the results gives comparatively uniform lines, considering the conditions. The samples were taken by the regular sampling-force of the works at 10-min. intervals, as shown in Tables I., II and III, which also give the chemical analysis of the samples so taken. The test shown in Table I. was made with a new converter; that of Table II with a converter that had made three charges and had been cleaned out; that of Table III with a converter that bad blown one charge to white metal, and had then been " washed " out and used for the test. In plotting these results, it was necessary to take, as a basis, the percentage of copper in the samples. This basis does not exactly represent the true condition, since the volume is constantly decreasing and a certain quantity of copper passes into the slag, but it is as near as can be obtained in practice. Take, for instance, in Table I., the sample No. 5, which shows : Cu, 59.9;

Jan 1, 1907

By C. W. Nicolson

THE Tri-State zinc and lead-mining district is in the northeast corner of Oklahoma, the southeast corner of Kansas and the southwest corner of Missouri. The area throughout which active mining has been conducted is about 45 miles long and about 5 miles wide, extending northeasterly from Commerce, Okla., to Alba, Missouri. Although the lead ores were mined on a very small scale in the vicinity of Joplin, Mo., as early as 1848, nothing of any importance was done in the district until 1870, since when both mining and smelting have been prosecuted with considerable vigor. In the beginning the lead ores only were exploited, but within a few years extensive deposits of zinc ores were found and since that time the production of zinc ore has far exceeded that of lead. Both the surface and mineral rights in Missouri and Kansas were under individual ownership by the time ore was discovered. Although some of these rights were purchased by mining companies, most of the mining has been done under leases covering small areas, usually 40 acres, although in the past many leases were given on much smaller tracts. In Oklahoma most of the mineral land had been alloted by the Government to various Indian tribes and although the title to some of these lands had been acquired by various white men before the discovery of the rich Picher field, the title to most of the land has remained with the Indian tribes and the leasing of the mineral rights has been done by the Federal Government for the benefit of the Indians. The Indian allotments were of 200 acres each and some of the mining leases covered entire allotments, although many leases were granted for only 40 acres or even less. Practically all of the leases granted in the past required the erection of a concentrating plant on each lease, a condition that has had a pronounced effect upon the mining and milling methods of the district, since the apparent ore reserves on each tract were too small to justify large

Jan 1, 1938

By Earl S. Greiner, Bradley Stoughton

As a part of the systematic study of the alloys of iron under the auspices of the Engineering Foundation, and preliminary to the commencement of comprehensive work on this larger subject, the authors have undertaken an investigation of the available literature dealing with the alloys of iron and silicon. The purpose is to collect all the data in English and foreign languages and present them in two monographs, one of a more scientific and the second of a more industrially useful nature. Of course, a great deal of information upon the constitution of the iron-silicon alloys was found specificially upon the changes of phase in the equilibrium diagram and the different phases present, such as solid solution, chemical compounds (iron silicides), etc. While no extended research was contemplated in the particular study undertaken, nevertheless the data collected proved to be so contradictory in many respects that a simple study of some of the outstanding problems involved in the constitution and equilibrium diagram was undertaken. Because research was not a primary object of the work, and also because of the extreme industrial importance of the silicon alloys between 0.80 and 14 per cent. silicon, and finally because of the unsatisfactory state of knowledge existing as to these alloys, the experimental investigation was limited entirely to alloys with less than 10 per cent. silicon. Discussion oF Continuous Series It has often been said in print that the iron-silicon alloys form a continuous series of solid solutions from 0 to 15 per cent. silicon. This claim the authors are inclined to doubt: first, because the alloys from 0 to 4.25 per cent. silicon are ductile and malleable at atmospheric temperature, while those with 5 per cent. or more of silicon are comparatively hard and brittle. Furthermore, the alloys with more than 4.25 per cent. silicon are comparatively hard and low in ductility at atmospheric temperature, but become much more ductile when heated slightly. It is well known, for example, that the alloy containing 4.75

Jan 1, 1930

By Charles Macdonald

It may seem to be almost unnecessary to occupy the time of the Institute in further consideration of a question which has been so comprehensively treated in papers already on file in our own Transactions and in those of the American Society of Civil Engineers. Unfortunately, however, the results of these concerted efforts have not been materially to increase our stock of Knowledge in the direction sought for; and as the necessity for this information is becoming.more and more apparent as the demand for structural materials increases, it is believed that by continuing the agitation by means of discussions in this and kindred societies, whose members are vitally interested in obtaining reliable data as to the properties of the materials they are called upon to work with, public opinion may be educated up to the importance of exerting such an influence upon the law-makers of the country as will result in the formation of a competent board, with adequate means at its disposal, to carry out this great work in a manner alike acceptable to the makers and users of the materials in question. It may be proper in the first place to glance briefly at what has been attempted thus hr, then to indicate some of the more important lines of needed investigation, and finally to consider reasons why government aid may with propriety be sought for in carrying on the work. At a convention of the Society of Civil Engineers held at Chicago June 5th, 1872, it was, on motion of General William Sooy Smith, resolved, that, " Whereas, American engineers are now mainly dependent upon formula for the calculation of strength of the different form of iron and steel, not based on experiments upon American materials and manufacture; and " Whereas, There differ greatly in many of their ch~racteristics front thoae of foreign production, both in their nature and forma: therefore,

Jan 1, 1882

By Ernest F. Burchard

The Pao deposits of iron ore are in the State of Bolivar, Venezuela, near Upata, about 30 miles south of the Orinoco River and 90 miles east of Ciudad Bolivar. They were discovered 4 or 5 years ago and have not yet been developed to the stage of mining. In March-April, 1929, the writer devoted a week to the examination of these deposits. The maps, drill records and chemical analyses presented herewith were derived from original sources, and the field photographs were made by the writer. The petrographic and metallographic data are from notes by C. S. Ross and M. N. Short, of the U. S. Geological Survey, who have kindly collaborated in these special phases of the study. The Iron Obebodies Topography and Accessibility The deposits are in a region of low mountains representing northern outliers of the Guayanan Highlands. These mountains reach altitudes of 1800 to more than 2000 ft. above sea level, as determined by aneroid barometer. The iron ore is found on mountain crests that reach altitudes of 1915 to 1930 ft., and may be followed down precipitous slopes for 200 • to 300 ft. or more. The greatest vertical range in outcrop is nearly 400 ft., and drilling has indicated that the ore extends to this depth below the surface in one place, at least. The superior hardness of the iron ore accounts for the preservation of the local mountain crests with the intermediate valleys eroded in softer granitic rock. The deposits of iron ore are reached by a private road for automobiles branching northeast from the Ciudad Bolivar-Upata road, a distance of about 12 miles. This road was used in 1928-29 by trucks for transportation of food and camp supplies, gasoline, drilling equipment, etc., but was not suitable for the transportation of iron ore. Between Ciudad Bolivar and the iron-ore area the western two-thirds of the automobile road passes through nearly level, open country known as the savanna, largely used for grazing cattle. About 96 km. (60 miles) east of Ciudad Bolivar at

Jan 1, 1931

By Aug. J. Jr. Bowie

(Read at the Wilkes-Barre Meeting, May, 1877.) Brief Outline of the General Topography of the Gold Regions of California. THE topographical features of California, as demonstrated by the explorations of the State Geological Survey, are found to be exceedingly simple. Three equidistant parallel lines can be used in conveying a general idea of the physical geography of Central California. A straight or " main axial line," whose course would be north 31° west, passing through the culminating peaks of the Sierra for a distance of five hundred miles, can be assumed as the eastern boundary of the State. A second parallel drawn fifty-five miles west of the " main axial line" will skirt the western base of the Sierra Nevada, along the edge of the foot-hills. A third parallel run equidistant from the second will represent "as nearly as possible the western base of the Coast Ranges." These parallel lines divide the State into three belts, namely, the Sierra, the Great Valley of California, and the Coast Ranges. " This arrangement of the physical features holds good for a length of four hundred miles in the direction of the main axial line, comprising almost the whole of the agricultural and the greater part of the mining districts."* The section of the country which is of immediate interest to the miner is the western slope of the Sierras. These mountains, rising in a short distance from the Sacramento plains to elevations of over seven thousand feet, with occasional peaks ten and twelve thousand feet high, are cut by numerous deep and precipitous gorges or capons, through which drains the immense watershed of the Sierra, supplying the main rivers of the State and ultimately emptying into the Pacific Ocean. Between these capons, ridges or divides are formed, on top of * See vol. i, p. 5, Geological Survey of California. J. D. Whitney, State Geologist.

Jan 1, 1878

By D. K. Crampton

INTERNAL stress and season cracking in brass have been studied for many years and the technical literature contains many data on various phases of the subject. A résumé of the literature shows certain fairly well established points upon which various authors are mostly agreed: 1. Season cracking is primarily caused by the presence of relatively high internal stresses, or possibly in some cases by external stresses, or both. 2. A specific corrosion is also essential to season cracking: Certain agents, particularly mercurous salts, mercuric salts and ammonia salts; have such a specific corrosive effect. 3. The tendency to season crack under given conditions increases with increasing zinc content, brass containing less than 20 per cent zinc being relatively immune. 4. In alpha brass the season cracks are intercrystalline; in alphabeta brass they lie between the two constituents; and in beta brass they are transcrystalline. 5. The ordinary impurities or added elements in special brasses have little or no effect on the tendency to season crack. 6. Internal stresses can be eliminated, or at least reduced to a safe 'limit by annealing treatments at temperatures that do not produce visible microstructural changes or appreciable softening of the worked brasses. There are, however, some points in connection with the phenomenon of season cracking which have not been thoroughly investigated, or wherein different authors and investigators are not entirely in agreement. The investigations described in this paper were undertaken to determine: 1. The correlation between mercurous nitrate tests and actual season cracking on long-time atmospheric exposure. 2. The quantitative effect of type and degree of drawing operations on the intensity of internal stress and on the tendency to season crack in brass tubes. 3. The possibility of drawing high-brass tubes in such a manner as to prevent the occurrence of harmful stresses rather than to find a remedy for such stresses once having obtained them.

Jan 1, 1930

By M. J. Sinnott, W. R. Kiessel

The creep characteristics of commercially pure titanium sheet in the annealed state, cold-worked state, and cold-worked and recovered state in the temperature range from 75' to 750°F have been determined. Titanium has been found to exhibit strain aging characteristics. The effect of strain aging on creep has been determined. A possible explanation for the poor creep properties of titanium is proposed. THE metal titanium exhibits many desirable properties but results on its creep properties have been somewhat disappointing. The creep strength is low even though the material has a very high melting point.' The present work was undertaken to determine the creep strength of titanium in various conditions; annealed, cold-worked, and cold-worked and recovered and to determine why titanium shows such relatively poor creep properties. The general procedure followed in this research consisted in obtaining the usual mechanical prop- erties such as creep strength, short time tensile strengths, and hardness on materials treated to a controlled degree of internal strain, as determined by X-ray diffraction measurements, and their subsequent interpretation in terms of this internal strain. The material used in this work was sheet stock taken from one heat of commercially pure titanium. As-received, this sheet was 0.060 in. thick. The analysis was given as 0.037 pet C, 0.023 pet Si, 0.50 pct W, 0.063 pct Ni, 0.08 pct Fe, and the remainder titanium. The oxygen and nitrogen were unreported but generally are about 0.2 pct in commercial heats. In order to put the material in a state of minimum internal strain all the sheet was given an anneal in a static argon atmosphere for 1 hr at 1600°F prior to processing and testing. The microstructure of the material after this treatment was essentially a single-phase solid solution of uniform equiaxed grains. For the studies on the cold-worked sheet, the material was reduced by rolling in a two high, 5 in. mill. Rolling was done at room temperature in passes

Jan 1, 1954

By Walter E. Duncan, Oscar F. Tangel, A. M. Gaudin, Franklin Dewey, R. A. Johnson

Xanthates have been used as collectors of sulfide minerals in the concentration of ores by flotation for over a decade, yet much remains to be done to elucidate the underlying reasons for the remarkable effectiveness of these compounds in this connection. Briefly stated, the known facts concerning the effect of these reagents on the floatability of minerals are as follows: 1. Xanthates are without effect on silicates, silica, and generally on minerals currently regarded as "gangues." 2. Xanthates in very small amount increase enormously the floatability of sulfides of copper, lead, silver, iron and mercury. 3. If zinc sulfides are first '(activated," as by treatment with a copper salt, they are readily floated by xanthates; otherwise not. 4. Elemental copper, silver and gold have their floatabilities increased by xanthates. 5. Sulfides of elements that are not typically metallic—e.g., stibnite, realgar, molybdenit—are not made to float markedly better by treatment with xanthates. 6. Oxidized minerals of lead and copper are floated if treated with large amounts of xanthates, but not so if treated with amounts of the same order of magnitude as required for sulfide flotation. Oxidized zinc minerals are not floated unless xanthates having unusually long hydrocarbon chains (e.g., eight carbon atoms or more) are used. Iron oxides and carbonate are not floated by xanthates. From a flotation standpoint the most striking feature about xanthates is the very small amount required to accomplish startling changes in the behavior of some minerals. The amounts used in practice to effect excellent concentration are frequently of the order of 0.05 lb, of agent per ton of ore; that is, of the order of one part of agent per forty thousand parts of ore. Changes in amount of agent of the order of 0.01 lb. per ton of ore (or 0.002 lb. per ton of pulp, on a 4:l basis) have marked effects on the metallurgical results obtained. Yet these changes represent a variation of but one part per million parts of pulp.

Jan 1, 1935

By Leland Russell van Wert

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

Jan 1, 1931

By R. L. Klueh, W. W. Mullins

During the course of a study on the periodic precipitation (Liesegang phenomenon) of water vapor bubbles in solid silver, some interesting observations were made concerning the formation and growth of these bubbles. Under certain conditions it was found that the bubbles which formed in the single crystals led to the formation of large blisters ad cracks, and when poly crystalline specimens were used grain boundary cracking was observed. These two phenomena were examined in some detail, and it was found that an important step in the formation of the blisters and grain boundary cracks was the impingement of neighboring bubbles. DURING the study of Liesegang precipitation in solid silver,' some interesting observations were made concerning the formation and growth of water vapor bubbles. The bubbles were formed by annealing oxygen-saturated silver in hydrogen. Because of the similarity of this phenomenon to the hydrogen embrittlement of tough pitch copper,' it is known in the literature" as the hydrogen embrittlement of silver. In some respects it appears that the hydrogen embrittlement of silver is similar to the processes of hydrogen attack of steel5 and blister formation.' Hydrogen attack results from the high-temperature reaction of hydrogen with dissolved carbon or carbides in the steel to form methane (usually at grain boundaries). Blister formation occurs in steel and other materials as a result of hydrogen produced by corrosion, pickling, and so forth. Because of these similarities, some speculations were made concerning these other processes. EXPERIMENTAL PROCEDURE Water vapor bubbles were formed in 99.999+, 99.99+, and 99.9 pct Ag by annealing in a partial pressure of oxygen (pq) until saturated and then in a partial pressure of hydrogen (pH,). The hydrogen diffuses into the silver and reacts with the dissolved oxygen to form water vapor which precipitates in the form of bubbles. The specimens were then sectioned, silver-plated, mounted in cold-setting plastic, ground and polished through a preliminary polishing, and finally chemically polished.' The bubbles were visible without etching.

Jan 1, 1969

By Robert Mehl

RELATIVELY few data have been collected on the rates of diffusion in ternary solid solution systems. In general it does not seem worth while to gather extensive data for such systems until the factors that determine the rates of diffusion in binary systems are better understood. But the rates of diffusion in a ternary system of limited solid solubility, in which the terminal solid solution is in equilibrium with an intermediate phase and may thus be represented as a quasibinary system, represents a case of special interest. In this case, where by reason of the association of the two solute metals in an intermediate phase a special attraction of the two solute atoms may be safely assumed, some interaction of these atoms during simultaneous diffusion in the solvent lattice might be expected. It has frequently been proposed that molecular solid solutions exist in quasibinary and in other ternary (and binary) solid solutions. There is no direct evidence for such solid solutions; arguments based upon the supposed anomaly in certain physical properties1 are hardly important; unexpected density relationships have proved deceptive ;2 suggestions of molecular solid solutions have been made on the basis of solution laws in their application to certain systems, but without result;3 attempts to find lattice parameters in the solid solution Al-MgZn2, which cannot be calculated from the separate effects of magnesium and zinc and might therefore be taken as evidence for a molecular aggregation, have given negative results.4 Fundamentally, methods for the determination of the state of molecu¬lar aggregation in solution depend upon the kinetic behavior of the par-ticles constituting the system. If it could be shown that the two solutes in a quasibinary ternary system diffuse in molecular proportions, despite a radical difference in the separate rates of diffusion of each solute when diffusing alone in the solvent lattice, some basis for the concept of molecu-lar solid solution would be afforded. Freche5 examined the rates of independent and simultaneous diffusion of magnesium and silicon in

Jan 1, 1939

Coal was known in this county before 1819, but there is no record of its use before that year. In that year a furnace, the first one built in the northwestern countries, was put in blast on Bear Creek; it was built to use coke and its first blast was with this fuel, which was made in heaps, but the blast was too weak and the furnace chilled after two or three tons of iron had been made. Charcoal was then substituted, and this use of coal ceased.1 In November of the same year a resolution was adopted urging state aid for a road from Kittanning to. Hamilton, New York: "that this road will increase the trade and industry of the whole county, between Pittsburgh and the New York line; and that our soil will in consequence be better tilled, our mines of coal, of iron and of salt, be better wrought, etc."2 In 1828 an advertisement of lands situated near Freeport on the Allegheny River and contiguous to the canal nearly completed between the Kiskiminitas and Pittsburgh stated that they contained "large and never failing springs, Coal in abundance, and a great deal of Fine Timber."3 In 1830 there were said to have been 24 salt wells in this county producing 327,000 bushels of salt, chiefly on the Kiski and Allegheny Rivers. In 1837 there were a number of wells in the vicinity of Freeport. As all the salt works on the Conemaugh River, were using coal long before 1830,4 it is safe to say that a considerable tonnage of coal was used for some years in these plants. In 1837 a tract of land in Clarion Township having a new saw mill and abounding "in Stone Coal" was offered for sale,5 and also one in Toby Township having "an abundance of the best quality of iron ore and stone coal."' In 1839 an advertisement in the Pittsburgh Mercury said

Jan 1, 1942

By R. G. Webber, F. C. Langenberg

During the course of some magnetic investigations which the authors have under way, six bars of 0.43-carbon steel were tested, a permeameter designed after the Hopkinson yoke type being used. The results obtained were of some interest and although far from complete serve at least to show the necessity for a careful investigation of the previous history of the samples under study as well as the chemical composition. A steel of given chemical composition may assume a great variety of structures, depending on its treatment. Professor Sauveur has devised a very clear and effective means of illustrating this point. The accompanying microphotographs show some of the possible structures assumed by a 0.30 carbon steel (Fig. 1). It is now a well-established fact that a structural change is accompanied by changes in the tensile strength, elastic limit, hardness, etc., and it seems reasonable to assume also, a change in the magnetic properties. Six bars of a 0.43-carbon steel were used, all the bars being taken from the same rod and treated as follows: Bar 1. Heated to 1,100° and cooled in the furnace. Bar 2. Heated to 1,000° and cooled in the furnace. Bar 3. Heated to 900° and cooled in the furnace. Bar 4. Heated to 1,000° and cooled in air. Bar 5. Heated to 900° and cooled in air. Bar 6. Untreated. The bars were then turned to 13 mm. diameter and tested by the Hopkinson yoke method. After testing, three specimens were taken from each bar, one from each end and one from the middle. The homogeneity of the bars was tested in this manner and in no instance could any difference in structure in the three specimens1 be detected. Bars 1 to 3 inclusive are pearlitic in structure. The white areas are ferrite (iron with certain impurities in solution) and the dark areas pearl-

Jan 1, 1915

By John Chipman

HE lecture on 'Thermodynamic Properties of Blast Furnace Slagso prepared in 1959 and published two years later required revision in one particular before it appeared in print. The activity of SiO, was deter mined through studies of the equilibrium: SiO, (in slag) 2C (graphite) = (in Fe) 2C0 (1 atm) The ratio for each experimental temperature was found from the heat of formation of cris-tobalite, the entropies and heat capacities of the re-actants, by virtue of the third law of thermodynamics. Discrepancies between several kinds of data led to investigations regarding other equilibria involving SiO, on the suspicion that there might be an error in the third-law value of its free energy. In particular the equilibrium: was restudied by Kay and Taylor who Confirmed the earlier results of Baird and Tayloron which their SiO, activities depended. The free energy of Sic was also rechecked4 independently. These and other equilibrium measurements led to the conclusion6 that the free energy of SiO, at high temperatures is in error and requires a correction of about -5 kcal. The exact source of the error is uncertain; it could lie either in the entropy of SiO, or in its heat of formation, but it more probably lies in the latter. Adjustment of this free energy lowers the ratio by a factor of approximately 4. Accordingly it will be necessary to multiply by this factor all of the SiO, activities determined by this method.',B Referring to the lecture cited, this correction should be applied in Figs. 8, 9, 10, 19, and 20. It applies also to the experimental data of Fig. 13, bringing these as well as those on the ternary system into good agreement with the work of Taylor and associates. At the same time it eliminates the discrepancy shown in Fig. 11, lowering both lines until the upper

Jan 1, 1962

By Charles C. Hawes

DETERMINATION OF SILICA OXIDE iron ores usually are found in intimate association with silica and phosphorus compounds. Their quantitative separation and purification sometimes present difficult problems to the chemist. Silicic acids may represent various degrees of dehydration. They are exeedingly weak, but combine with metallic oxides and form some of the most stable oxides in nature, the silicates. When iron ores are treated with hydrochloric acid, they yield practically all their iron. However, apart from rare exceptions, varying amounts of insoluble residues of silica, alumina, lime, magnesia and compounds of phosphorus, sulphur, titanium, chromium and others will be left. If the oxides of silicon, aluminum and titanium are present in small quantities, the insoluble residue is generally very small, but the presence of these oxides is more usual in larger quantities. Therefore, only a special treatment can break the bond between these elements. Ore Residues Acids remove the soluble constituent of the ore, leaving the insoluble residue, which chemically is rock or gangue and must be treated accordingly. Alkali carbonates are used frequently to break up the residue, but other fluxes have also been recommended, such as a number of lead and boron salts. The introduction 0f these salts, which offers certain advantages, requires, however, their removal before the other constituents can be analyzed, and this elimination is sometimes difficult. Usually in quantitative analysis silicates are dissociated by fusing them in a platinum crucible with sodium carbonate, thereby forming sodium silicate, Na2SiO3, sodium aluminate, Na2Al204, sodium titanate, Na2TiO3, and carbonates of other elements. All the carbonates are soluble in hydrochloric acid, but also some silicic acid is formed that must be rendered insoluble. To this end the solution is evaporated several times, as the first evaporation still leaves as much as 5 per cent of the silica soluble. Even after a number of evaporations, minute quantities of silica may be found with the iron and alumina present. Perchloric Acid as an Agent for Dehydrating Silicic Acid Perchloric acid, HC104, (60 per cent), has been used for years as a solvent, but few chemists have used it to dehydrate silica. It is derived from anhydrous perchloric C1207, which is most unstable and dangerous. Perchloric acid is a strong oxidizing agent, which boils at 203°C. It is more effective in rendering silica insoluble than any other known agent, and most rapid in action. After perchloric acid is added to a mixture containing silicic acid, the resultant solution is

Jan 1, 1945

By Leland Van Wert

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

Jan 1, 1931

The early records of coal in Kentucky by Walker and Gist have already been mentioned. Thomas Hutchins was aware of it in 1778, or perhaps several years earlier, as in writing of the Buffaloe, now Green, River, he said, "several persons who have ascended this River, say, that Salt Springs, Coal, Lime and Free Stone etc. are to be found in a variety of places."1 The next record found is an entry to Ellis and Marshall, of 878 acres on Coal Bank Creek, in the, then Fayette County on July 14, 1784.2 The settlement might have been made, or the name given, some time before. Hermeline, in 1783, mentioned iron ore and coal on the Green River,' although he had not been west of the Susquehanna River; his knowledge of coal might have come from Hutchins, although the latter made no mention of iron in that locality. In November 1790, coal was mined on Sturgeon's Creek in Lee County and floated in three barges down the Kentucky River to Cleveland's Ferry, where it was hauled to Lexington. The results were not equal to the expectations, and it was 1793 before the experiment was. repeated 4 In 1791, the estate of Samuel Wharton advertised for sale 31,000 acres "in the county of Jefferson, on the North Side of the Green or Buffaloe river, in the State of Virginia."5 In November 1795 three patents were issued for land in the then Lee County, aggregating 130,000 acres. These patents cover much of Harlan County. The descriptions of these surveys mention passing stone coal. on Rough Branch of Martin's Fork, a "great deal of stone coal" on Blacksnake Branch of Pucketts Creek, and "a quantity of stone coal" probably on Crummies Creek.6 Jedediah Morse, in The American Gazetteer, 1798, said that in Kentucky "in many places there are appearances of potter's clay, and coal in abundance." It is possible that shipments may have been made from near

Jan 1, 1942