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By Paul Sterling

The general impression regarding the preparation of merchantable anthracite is that it is confined to a colossal, grimy structure, called a " coal-breaker." This name is a misnomer; for the desired result is not to break the coal, but to prevent its being broken. Preparation may be said to begin at the face of the chamber, with the mining and loading of the coal. Local conditions vary, not only ill the same field or basin, but also in the same mine, so that there is no fixed empirical rule governing the method of blasting or cutting coal. Tests should be made, when possible, to determine the explosive, or the mechanical coal-cutter, which will produce the largest percentage of what are locally known as " lump " and " prepared sizes " of anthracite. The prepared sizes are those mostly consumed for clomestic purposes. All other sizes might be called by-products of the anthracite industry; for they are not especially desirable, being the degradation resulting from the mining and handling of a brittle or laminated material. Being low in volatile combustible matter, anthracite burns most successfully when nearly of a uniform size, permitting the easy passage of air through the voids. This accounts for the large number of sizes into which the coal is separated. Table I. gives the various sizes, the diameter of ring over and through which each size is made, and the usual purpose for which it is employed.

Jan 1, 1912

By Robert T. Hill

The successful completion, January 10,1901, by Capt. A. F. Lucas, of a well, near Beaumont, Texas, whereby an enormous flow, estimated at '75,000 barrels a day, was obtained, opened a new oil-field in the United States, kindled a frenzy of exploitation and speculation, revolutionized the fuel industry of a large region, and brought gain to thousands of people. Even to-day, it is impossible to cast up the present results or to prognosticate the future influence of this event. It has caused the revival of attention in other localities where oil had been suspected, and exploration for oil throughout the Texas region. It has attracted notice to the mineral resources of the Texas region, and created an interest in the geological conditions of that great State. This State, which has increased in population and wealth, as recorded by every succeeding census, with leaps and bounds such as are exhibited by no other part of the Union, now stands fifth in population and first in productive wealth per capita. Its fields, pastures, forests and mines teem with raw material. The whole economic evolution of the State has gravitated toward a focal point where these products were available for the coming of the kiln, the machine and the factory. The only drawback to the prosperity of the State was the lack of an economic fuel, inferior coal costing an average of $5.00 per ton at the time of the Beaumont discovery. This

Jan 1, 1903

By E. C. Bain

THE more familiar compositions of iron-carbon-chromium1 and the iron-carbon-tungsten2 systems have been investigated with a degree of thoroughness which has permitted the construction of their three-dimensional equilibrium diagrams; and it is probable that these equilibrium diagrams are sufficiently accurate for the present metallographic needs. Strangely enough, in spite of their importance, the alloys of iron, carbon and manganese apparently have not been investigated in the same systematic manner, and so far as is known, no three-component equilibrium diagram for this system is available. Even iron-carbon-nickel alloys3 have been studied rather more thoroughly; for these the solidus and liquidus surfaces have already been determined, but the solid transformations in this, as in the manganese system, have not been reported systematically. The present paper deals with the constitution at equilibrium of a series of 36 iron-carbon-manganese alloys of commercial purity limited by 1.5 per cent carbon and 15 per cent manganese, a range of compositions including most of the manganese steels. The temperature range of melting has not been determined, nor has the high-temperature (delta iron) ferrite equilibrium been included in the study, it being considered that the more important characteristics of the manganese steels are their ordinary transformations in the solid state. The delta iron region is almost certain to be a small tetrahedron not very different in magnitude or contour from that in the iron-carbon-nickel diagram. It is probably true

Jan 1, 1932

By W. R. Shimer

(New York Meeting, October, 1913.) THE investigation herein described was carried out for the purpose of studying, both by chemical and metal-lographical means, the extent of over-oxidation of steel that can be accomplished by excessive over-blowing in a Bessemer converter. In addition there are appended some results of basic. open hearth and crucible steels. Remarks on Chemical Methods. The test block used was hemispherical in shape, 4.5 in, in diameter and 2 in. thick. Drillings for analysis were obtained by drilling through the entire solid part of the. block, carefully avoiding all cracks anti blow-holes and mixing these drillings thoroughly. Drillings were carefully examined for scale and the finest were gone over with a microscope to be sure all scale from whatever source had been. removed. Oxygen was determined by the well-known method of Ledebur, modified according to Cushman,1 with, however, the removal of the preheating tube, which was found unnecessary. This method has been found to give concordant results. Blanks run from 0.0003 to 0.0006 g. Duplicate determinations varied not more than 0.001 to 0.003 per cent. It seems to be generally supposed that the hydrogen method gives only that oxygen which is combined with iron. Whether this be true or not, the content of oxygen existing as iron oxide no doubt predominates sufficiently, so that the result obtained is sufficient to indicate whether the steel is over-oxidized or not.

Jan 9, 1913

By H. A. Bedworth

ALLOYS of copper and silicon have been known for one hundred years or more but the commercial development of this type of alloy has taken place during the past few years. In 1905, Sperry1 proposed the use of copper-silicon alloys for springs and other purposes for which copper-tin bronzes were used. Some attention was given to this proposal at the time but no one succeeded in producing a practical alloy containing more than a fraction of a per cent. of silicon. The equilibrium relations of the copper-silicon system were studied first by Rudolfi2 and later by Sanfourche3 and Corson.4 The constitution of the system has also been recently investigated by Matuyama,5 and in the laboratories of the American Brass Co. by Smith.6 Some of the physical properties of the copper-silicon alloys have been investigated by Norbury7 and by Geiss and Van Liempt.8 Summarizing the results of various investigators of, the constitution of copper-silicon alloys, the solubility reaches its maximum value, 6.7 per cent. silicon, between 721° and 782° C. At 852° C. the solubility is 5.25 per cent., while at 400° C. it is only 4.1 percent. silicon. The copper-silicon alloy begins to get so hard at about 3 per cent. silicon that it is difficult to manage. It was found by Jacobs that the addition of manganese to this alloy considerably improved the working

Jan 1, 1929

By Virgil R. D. Kirkham

NoRth America has for many years led the world in phosphate production, but with development of African deposits and their marketing conditions with respect to European countries, this leadership will shortly pass to Africa. Algeria, Egypt, Tunis, and Morocco have large phosphate reserves and a correspondingly large production because of easy mining and a ready European market, which was developed during the war. An increase in home consumption is destined to develop for the eastern American fields, and the countries of the Pacific will provide a market for the western producers. New processes indicate a decrease in fertilizer costs, which will encourage a more widespread domestic use and assure better marketing conditions. The African deposits, although benefited by a water haul, have the disadvantage of being isolated from a source of acid so that the crude rock is shipped from Africa to its destination, whereas in the United States the chief product shipped is acidulated rock or various types of superphosphatic fertilizers, The principal types of phosphate deposits used in the manufacture of fertilizers are guanos, apatite, phosphatic marl, phosphatic limestone, phosphatic shale, and phosphate rock which is also known as phosphorite. Some of these deposits are found on each of the continents; Table 1 gives their occurrence, age, location, character, extent, etc. Most of the information found in this table represents a compilation of information published elsewhere in a different form and widely scattered.

Jan 1, 1925

By Frederick F. Frick

SPONGE iron as produced at Anaconda is a fine, -35 mesh, impure product, about 50 pct metallic iron, obtained from the reduction of iron calcine at a temperature of 1850°F by use of coke resulting from slack coal. The metallic iron particles are bulky and spongey and precipitate copper readily and rapidly from a copper sulphate solution. Investigation of the treatment of Greater Butte Project, Kelley, ore at Anaconda early showed the desirability of using sponge iron as a precipitant for the copper in solution resulting from desliming of the ore in a dilute sulphuric acid solution. Anaconda had done considerable work on the production of sponge iron in 1914 for use as a precipitant of copper from leach solutions. Some success and considerable experilence were attained at the time. indicating that, sponge iron might be successfully made by a modification of the process used in 1914, a batch process in which an iron calcine was reduced by means of soft coke, resulting from noncoking coal, in a Bruckner-type revolving horizontal cylindrical furnace widely used 50 years ago. The coke and calcide formed the bed in the Bruckner furnace, which was rotated at about 1 rpm. The bed was brought to a temperature of about 1800°F by means of an oil flame over the surface. Although results were reasonably satisfactory, they did not warrant full development of the process at that time. A good deal of work has been done in the last 50 years on the production of sponge iron. The objective in some cases has been the production of a precipitant for copper from solution, but the bulk of the work has been done for the production of open-hearth steel furnace stock. The production of an open-hearth stock presents two problems rather than one: first, producticon of the sponge iron, and second, what is perhaps of equal difficulty and importance, conversion of the sponge iron into a form suitable for use in the open-hearth furnace. So far as is known to the writer, none of the sponge iron processes tried in the past have proved to be economically feasible. However, Anaconda had a combination of conditions appearing to justify an attempt to produce sponge iron which would serve for the leach-precipitation-float process. It was thought that the process used in 1914, if changed to a continuous one, might work out satisfactorily. The following favorable conditions at Anaconda justified the investigation: 1—A sufficient tonnage of good grade iron calcine resulting from the roasting of a pyrite concentrate in one of the acid plants, at substantially no cost. 2—Reasonably cheap natural gas. 3-—The fact that there was no need for production of a high grade product. 4— The fact that there was no need for obtaining a consistently high reduction of' the iron in calcine. A small revolving Bruckner-type furnace about 2 ft ID by 4 ft long was set up for early pilot work at the research building. This pilot furnace showed that a satisfactory product could be obtained at reasonable cost. It also indicated a marked advantage in preceding the reduction furnace with a furnace of similar size and capacity for preheating and roasting out any residual sulphur from the feed. The small furnace was operated for several months, various details of the process were worked out. and sponge iron was produced to supply a pilot LPF plant which treated 300 lb of Kelley ore pel- hr. Later a second pilot furnace 5 ft in diam and 12 ft long inside was set up at our reverberatory furnace building. This furnace confirmed the data of the small furnace and gave a basis for design of the final plant. At Anaconda a pyrite concentrate, running about 48 pct S, is recovered from copper concentrator tailings by flotation. This concentrate is roasted to sulphur of 3 pct or less at the Chamber acid plant. The iron calcine contains about 57 pct Fe and 18 pct insoluble. The iron calcine feed, as mentioned before, is re-roasted and preheated in a reroast furnace preceding the reduction furnace. Both are of the Bruckner type. The reroasted calcine is fed into the reduction furnace at 800" to 1000°F along with 30 pct slack coal. In the feed end of the furnace the volatile is burned from the slack, giving a soft coke which readily serves for reduction of the iron. Hard metallurgical coke will not serve the purpose. since it does not reduce CO readily at a temperature of 1850°F. All indications are that the actual reduction of the iron is accomplished by carbon monoxide below the surface of the bed, which is 30 in. deep at its center. Apparently there is a constant interchange: Fe²O³ + 3CO = 2Fe - 3CO², CO² + C = 2CO Actually iron oxide is reduced by CO at somewhat lower temperature than the 1850 °F used in the process. but this temperature is necessary to obtain a satisfactory rate of furnace production. The furnace atmosphere is generally reducing, and typical blue carbon monoxide flames satisfactorily cover the bed. Gas flames from four 3-in. Denver Fire Clay Inspirator burners are played directly on the bed, which is slowly cascaded by the 1 rpm of the furnace. An excess of coke is necessary to assure maintenance of good reducing conditions in the furnace bed. Part of this coke is recovered for re-use.

Jan 1, 1954

By A. Simkovich, R. W. Lindsay

The possibility of using sodium sulfide slags to remove copper from ferrous alloys has been investigated by Jordan1 and by Langenberg.2, 3 In these studies, such slags were determined to be capable of removing copper and sulfur from the melt. The present work represents additional effort to clarify the effects of temperature on copper removal. The experiments were performed in a 17-lb induction furnace. Graphite crucibles contained the melts and kept the baths saturated with carbon. Temperatures were measured with a calibrated optical pyrometer and were controlled by manipulation of power input to the furnace. Estimated accuracy of temperatures in this investigation is ± 10°C (18°F) for measurements prior to slag additions, and + 20°C (36°F) after slag formation. The procedure consisted of melting 800 g of electrolytic iron. During this step, powdered graphite covered the exposed iron surface. After a predetermined temperature was reached, copper shot was added. A sample of the molten alloy for chemical analysis was then aspirated into a silica sheath. Next, a slag-forming mixture of sodium sulfite and graphite was added instantaneously to the melt. The sodium sulfite amounted to one-tenth the charge weight of iron; sufficient graphite was added to combine with oxygen in the sodium sulfite, assuming formation of carbon monoxide and reduction of the sulfite to sulfide. Subsequent to the slag addition, the molten alloy was sampled periodically, with the exception of heat A in which no intervening samples were taken between the slag addition and the end of the run. The iron was poured into a graphite mold, and the ingots sectioned and drilled for samples. Results of selected heats are presented in Table I. Analyses of samples drawn from the iron prior to slag addition are listed under zero time. Two samples from heat D were reported with copper contents greater than the initial concentration in the bath. Owing to the gradual but complete disappearance of slag during this heat, it is believed copper momentarily became more concentrated in the upper portion of the bath while reverting from the slag. This is the region from which samples were drawn. It should be noted that analysis of the ingot was equal to the copper content at the time of slag addition. The terminal temperatures of heats D and E, and the initial sulfur content of heat A are also to be noted. Because of the large temperature drop which occurred when slag was formed in heat D, power input to the furnace was increased in heat E after the slag addition, causing a higher terminal temperature. In heat A, the initial sulfur concentration was relatively high as compared to heats B through E owing to contamination by some slag remaining in the crucible from a previous heat. It is evident from Table I that copper was removed at the onset of slag formation. Roughly 30 pct of the copper was taken into the slag, with the exception of heat D, which had approximately 50 pct removed. For a comparatively short time of slag-metal contact, it appears that no gain is to be made in copper removal through use of high or low temperatures. If the slag initially formed remains in contact with the iron for an extended period, temperature has a marked effect upon copper removal, as can be seen by studying results for the two extremes in temperature. At about 1425°C, the copper level remained relatively constant after the initial removal by the slag. However, in the region of 1670°C, a definite reversion of copper occurred. Reversion was incomplete in heat D, and complete in heat E. The final temperatures of heats D and E differed by about 75°C. This temperature difference is thought to be the reason for only partial copper reversion in heat D. It is believed the effects of temperature noted above are related to the evolution of a white fume, which appeared in every run except heat A. (In the case of heat A, the fume was practically indiscernible.) After each slag addition, a yellow flame formed for about 5 sec. When the flame subsided, a white fume appeared. Upon contact with surrounding cooler surfaces, this fume deposited as a white solid. In the experiments made at 1425°C, evolution of fume continued unchanged to the end of the runs. However, heats D and E exhibited a different behavior. A very noticeable decrease in fume evolution from heat D was observed. Furthermore, this heat had much less slag remaining than did runs A through C when the experiments were terminated. No slag remained at the end of heat E; evolution of fume from this heat ceased prior to pouring. Spec-trographic analysis of the white deposit indicated sodium to be the major metallic element, with the maximum concentration of iron and copper as 0.1 and 0.01 pct, respectively. It is supposed the white fume observed in these experiments is principally sodium oxide (Na2O), formed by oxidation of sodium in the slag and subsequent sublimation. (Sodium oxide is a white to gray substance in the solid state; at 1275oC, it sublimes.4) According to this mechanism, elevated temperatures would accelerate removal of sodium from the slag, sulfur pickup by the

Jan 1, 1961

By J. Quigley

As the outcrop mines in the West developed into underground operations, systems of ground support were gradually evolved. In the early coal mines there was little need for support except near the dirt line in portals, where stone masonry was common. Where the top was shaley or broken, native pine props with light cross bars and legs furnished enough support even in Utah's 25-ft coal seams. As depth of workings increased. roofs and backs of the same general nature as those near the surface became more and more unstable and required more and more support. Some coal airways show this tendency very clearly. From the surface down the same type of roof shows deterioration which an experienced eye can translate into a measure of depth under surface rather than change in rock characteristics. Rock bolts, developed by various companies and by the U. S. Bureau of Mines, have become an effective substitute for timber in sections of some metal and nonmetal mines formerly requiring escessive timber support, and further use of war surplus landing mats, chain link fencing, and a new punched channel developed by one of the steel companies has enabled other mines to operate deposits where costs of timber and lack of clearance for timber support would have prohibited mining. The block caving mines have made extensive use of reinforced concrete underground to achieve similar ends under difficult conditions. Steel sets are standard in many Bureau of Reclamation projects, although these are usually covered in with concrete to make the permanent structures the Bureau's reclamation projects require. But the use of steel in mining operations is limited and has been confined principally to the iron ore mines of Michigan, Wisconsin, and Minnesota. Some mines have installed used rail as posts, caps, and crossbars, but a rail section is not suited for load carrying, and used rails are generally brittle. having a tendency to fail without warning when overloaded. European mines were the first to reach the size of worked out areas and depths of cover resulting in major roof problems. The Europeans resorted to pack walls and masonry walls, in conjunction with timber arched sets. rail arches, and combination timber and rail and steel arches. The give in these pack walls and wooden blocking was supplemented by a hinge in the center of the arch. This design is called an articulated arch Through various refinements of this principle of the support giving graduallv with the load. Toussaint-Heintzmann developed the yielding or sliding arches, in which yield is accomplished by friction in the overlapping joints of the arch. This type has gained widespread acceptance in the Ruhr and Lorraine Basin and is being manufactured by Bethlehem Steel for sale in this country. In North America the anthracite mines in Pennsylvania, followed by certain iron ore mines in upper Michigan and Canada, were the first to employ these arches to any extent. The practice was later adopted by Kennecott at Ruth, Nev., and by others. Despite high initial cost, the use of these arches is growing in many parts of the country because of their suitability in heavy ground. In its present form of manufacture the yield-able arch consists of open U-shaped rolled section with heavy beads on the edge. The open edge of the U is placed toward the wall. The section nests in another section of the same dimensions, and an arch can be built up from rolled radii and tangents of various weights and lengths. Sections are fastened together by U bolts and saddles. The lap on the joint varies from 12 to 24 in., and ordinarily the bolts are tightened with a 1-in. drive air wrench. The arches are spaced with channel struts held by J bolts and saddles. Sections can also be obtained that are composed of various combinations of radii and tangents and true circles. The joints can be placed to bear against anticipated loads and asymmetrical loads imposed by dipping strata. In the arches now being manufactured clearance widths up to 19 ft are obtainable in weights of sections from 9 to 30 lb per ft. The circular cross sections are available in the same weights ranging from 8 to 16 ft diam. At present most of the arches sold are supplied only in carload lots. It is hoped that demand will grow so that distributors can stock various weights and sections to give small operators a chance to try this new type of rock support under their own particular conditions. Several excellent papers have discussed the properties of various sections now manufactured, the dimensions of the sets obtainable, and their application under widely differing conditions. The present article will describe the methods and results of a special use of the arches at Kaiser Steel mine No. 3. Sunnyside, Utah. Problem at Mine No. 3 : In 1953 Kaiser Steel Corp. laid out Sunnyside mine No. 3 to recover coking coal left by the previous operator, Utah Fuel Co.. below workings that had been abandoned in 1928. Two seams had been worked, the upper and lower, separated by 30 to 42 ft of rock. Approximately 10 million tons of coal had been extracted from this area some 3000 ft down the itch from the outcrop to a 1500-ft depth of cover. The mine had been opened by slopes in both upper and lower seams. Sometime in the late 1920's the lower slope

Jan 1, 1960

By George W. Mitchell

THE property of Eureka Corp. Ltd. is located in the approximate geographic center of Nevada, 2 miles from Eureka, the county seat. The great sources of power, the Colorado, Snake, and Salmon Rivers and the rivers of northern California, are 300 to 500 miles distant, and no lines serve areas closer than 150 miles. Fuel for diesel and steam generation is available in Utah, 300 to 400 miles to the east. Eureka's railhead is 80 miles north where two trunk lines cross the county. A spur line serves Ely, 77 miles east. Good highways connect Eureka to the railheads. Activity in the Eureka mining district began in the early 1870's. The oxidized high grade lead-sil-ver-gold ore terminated against the footwall of the Ruby Hill fault, and in 1890 the main operations ceased. In 1938 Eureka Corp. Ltd. discovered ore in the hanging wall of the fault by diamond drilling. The history of Eureka in the late 1800's indicates that there was some water at 600 to 800 ft in the old workings, probably accumulations above the water table which did not seriously interfere with mining operations. Both the Locan and Richmond shafts were sunk to a level below the table, but apparently the only serious difficulty with water occurred in the Locan. The steam pump used when the last work was done on the 1200 level in 1923, many years after exhaustion of the main orebodies, is still installed on the Locan 900 level. The capacity was about 500 gpm, lifting 750 ft to the 100 level, which connected with the surface. In addition to this. bailers were used to keep the 1200 level free of water. It is said that pumping in 1923 lowered the water in the Holly shaft, about a mile and a half away, but this seems doubtful. The pumping was of short duration because no ore was found. When work at the new Fad shaft was started in 1941 Eureka Corp. Ltd. engineers were fully aware of the probability of encountering water in large volume. Their primary exploration and development had to be carried on at the 2250 level. The first water was encountered at 300 ft. This was undoubtedly surface drainage in the bedding of the Pogonip limestone and was less than 100 gpm. The fractured, loose Hamburg dolomite at the water table was not well cemented, and relatively little water, 300 gpm, percolated through it with difficulty. At 1350 ft well-cemented dolomite containing some open fractures was encountered. These fractures produced the first water of consequence, 750 gpm. At 1700 ft the volume was 1000 gpm increasing to the maximum during shaft sinking, 1600 gpm, at the 2000 level. Secret Canyon shale, a dry formation, was entered at 2100 ft, where a concrete water ring was placed to catch all of the water. The volume decreased rapidly to a constant flow of 1200 gpm. Below 2100 ft the shaft and stations remained in the shale and water was not a problem. Several faults of moderate displacement, including the reverse Martin fault, had been intersected during the traversing of 1000 ft of wet Hamburg, but no undue quantities of water were encountered. Observations in the diamond drill holes in the ore zone area showed a rapid lowering of the water table. The shaft was flooded when it left the dry shale and entered the water-bearing Eldorado dolomite on the 2250 level, crossing a fissure which paralleled the Martin fault. High pressure water doubled the volume then being pumped. Pipe failure through a water door bulkhead was a contributing factor. Immediately following this flooding in March 1948 preparations were made to recover the shaft as rapidly as possible by increasing power and pump capacities as needed. Measurements before flooding indicated the water could be lowered at a fast rate. However, the water table did not recede as rapidly as expected and volumes required to lower the water in the shaft were higher. Obviously the size of the main water channel on the 2250 level was increasing because of erosion, allowing greater volumes to enter the workings and draining beyond the cone originally being drained during shaft sinking. Eroded material was being deposited in the shaft below the 2250 level in serious proportions. In December 1948 a second flooding of the Fad shaft was allowed for the purpose of reassessing existing conditions and studying alternate methods of attack. The detailed geology of the Eureka mining district, see Fig. 1, has been described during the past 75 years by many geologists.' Only the general features and those which seem to affect the drainage problem will be discussed. The old ore zone, mined between 1870 and 1890, is located in a wedge-shaped block of Eldorado dolomite between the footwall of the Ruby Hill fault and the underlying Prospect Mountain quartzite, see Fig. 2. Production of high grade oxidized lead ore containing high values in gold and silver has been variously estimated at $50 to $90 million. The tonnage mined was probably close to 1,500,000, nearly all of which was found above the water table. The new ore, discovered by diamond drilling in the hanging wall of the Ruby Hill fault, is a flat-

Jan 1, 1954

By William M. Boorstein, Robert D. Pehlke

The rates of solution (of hydrogen in liquid pure iron and in several liquid binary iron alloys were meas-ured using a constant volume technique. The rates of absorption and desorption were found to be equal un-der all experimental conditions. increasing concen-trations of S, Si, or Te decrease the rate of hydrogen uptake but additions of Al, B, Cr, Cu, or Ni have no measurable effect up to concentrations normally en-countered in steelmaking practice. No relation ship was found between the effect of an alloying element on the equilibrium solubility of hydrogen in liquid iron and its effect on the solution rate constant. Mathe-rnatical analysis of the data indicates that under the present experimental conditions the rate of reaction of hydrogen with liquid iron is controlled by transport of gas solute atoms in the metal phase. Comparison of the present resuts with data on nitrogen taken un der similar conditions establishes that the hydrody-nurnic conditions which exist near the surface of a metal bath are best approximated mathematically by a surface renewal model for the case of rapid in-ductive stirring and by a boundary layer model for more quiescent melts. HYDROGEN has long been recognized as being a detrimental constituent in steel. If dissolved in the molten metal in excess of its solid solubility, hydro-gen can be evolved during solidification and cause bleeding or porosity in ingots and castings. In the solid metal, lesser amounts play a definite role in causing other defects such as hairline cracks, blisters, and embrittlement. For significant refinements to be made in metallurgical procedures designed to control or eliminate hydrogen from liquid iron or steel dur-ing processing, available equilibrium solubility data must be supplemented with reliable fundamental in-formation pertaining to the kinetic factors involved in the transfer of hydrogen to or from the metal. The scarcity of such information in the literature prompted the present investigation. PREVIOUS RESEARCH Whereas much of the existing data on the solution kinetics of gases such as nitrogen were obtained during the course of thermodynamic investigations, the solu-tion rate of hydrogen has been found too rapid to be accurately determined by conventional solubility meas-urement techniques. Consequently, little work on hy-drogen solution kinetics has been reported in the lit-erature. Carney, Chipman, and crant1 attempted to study the rate of solution and evolution of hydrogen from liquid iron by employing a newly devised sampling method. Although no significant quantitative data could be obtained, it was observed that the rate of solution was approximately equal to the rate of evolution of hy-drogen from the melt. Karnaukov and Morozov2 stud-ied the rate of absorption and Knuppel and Oeters3 the rate of desorption of hydrogen from molten iron by measuring pressure changes with time in a constant volume system. Karnaukov and Morozov determined the hydrogen pressures over their inductively stirred melts with the aid of a McLeod gage and therefore, were forced to work at pressures not in excess of 40 mm of Hg. Their experimental data conformed to a mathematical correlation based on diffusion control: and the rate coefficients calculated on this basis were shown to be independent of the initial absorption pres-sure. These authors reported the solution rate of hy-drogen to be eight-to-ten times higher than they had found for nitrogen in a previous study. They also re-ported that under identical conditions, hydrogen dis-solves somewhat more slowly in iron-columbium alloys than in pure iron. Knuppel and Oeters found that the desorption of hydrogen from pure iron at 1600°C was controlled in all cases investigated by diffusion in the metal bath as long as bubble formation was sup-pressed. This was substantiated by Levin, Kurochkin, and umrikhin4 who studied the kinetics of hydrogen evolution from liquid (technical) iron while applying a vacuum. Salter5 measured the rate of hydrogen ab-sorbed by iron buttons, arc-melted by direct current, as a function of hydrogen partial pressure in a hy-drogen-argon atmosphere. A carrier gas technique was used for analysis of the hydrogen absorbed. The initial rate of absorption was found to increase di-rectly with the square root of the partial pressure of hydrogen. EXPERIMENTAL METHOD Because of the rapid uptake and evolution of hydro-gen by iron-base melts, a constant volume technique was devised in order to obtain meaningful kinetic data over the entire course of the solution process. Apparatus. A schematic view of the experimental apparatus is given in Fig. 1. The hydrogen-liquid iron reaction system consisted of a gas storage bulb con-nected to a meltcontaining reaction chamber through a normally-closed solenoid valve. The gas storage bulb, an inverted 250 ml round-bottomed Pyrex flask was joined to the inlet port of the solenoid valve by a glass-to-metal seal. A more detailed illustration of the reaction chamber is shown in Fig. 2. The design of the Vycor reaction bulb was essentially that de-scribed by Weinstein and Elliott6 with the exception of a shorter, larger diameter gas inlet for this kinetic study. In position, the reaction bulb was closely by an eight-turn coil of water-cooled copper tubing which, when energized by a 400-kc oscillator, provided the inductive heating source. The walls of the bulb were maintained relatively cool by circulating cold water along their outer surface, thus preventing

Jan 1, 1970

By C. S. Sivaramakrishnan, Manjit Singh, Rajendra Kumar

Regarding liquid nzetals structurally as a suspm-sion of clusters , having derivated solid-state coordination, in truly liquid atoms, the recently developed Kuvlar-Samarin technique of centrifuging- in liquid state enabled the determination of the cluster sizes inAl-Cu mid Pb-Sn systems. It is shown that the colutne fraction of the clusters does not exceed 9 pct and the energy of their formation in Al-Cu is about 5.5 kcal per g-atom and in Pb-Sn eutectic alloys about 25 kcal per y-atoni. STRUCTURAL investigations of liquid state have principally followed the following three courses: i) studies with X-ray, electron, or neutron diffraction; these investigations have shown that there is a certain amount of regularity in the structure of liquid metals which can be defined by a coordination number and that the structure is a derived function of that in the solid state; ii) thermodynamical investigations which are based on the concept of ideal behavior; these describe the liquid state in terms of free-energy values and other thermodynamic functions; although these investigations are of help in the study of the general effects of alloying, they do not provide any structural insight into the precise atomic distribution in liquid state; iii) measurements of surface tension and viscosity; although it is natural to expect that the viscosity is related to the structure in liquid state, these investigations have so far only provided information which can be used by the foundry technologists and has been little utilized in formulating models of the structure of liquid state. As it happens, investigators in the three groups have worked almost independently of each other and there is practically no structural correlation between the results of one group with those of another. The purpose of the present paper is to indicate that the experimentally measured parameters of these three groups of research are closely related to the structure in the liquid state. STRUCTURE OF LIQUID METALS Although atomic distribution in solid and gaseous states is rigorously known, that of the liquid state is only appreciated on the fringes. There is no universal model of atomic distribution in liquid state, but two diverse models are at present hotly contested. The first, largely expounded by ~ildebrand,' regards the liquids as condensed gas since many of their properties and much of their behavior can be adequately described by regarding them as fluids. The second mode12j3 considers that some form of near-solid as- sociation of large number of atoms exists in the liquid state. On the other hand, ~ernal' was able to predict rather precisely the radial distribution functions in liquids on the basis of statistical geometric approach which considered that liquids are "homogeneous, coherent, and essentially irregular assemblage of molecules containing no crystalline regions or holes large enough to admit another molecule". He introduced the concept of pseudonuclei in the otherwise random structure as aggregates of closely packed tetrahedra which gradually merge into irregularity and continually replace each other. To what extent the pseudonuclei can be regarded as regions of near-solid association is indefinite but Bernal suggested that the concept of pseudonuclei can be compromised with the latter model if the near-solid associations are regarded as extremely dense and not necessarily crystalline. The difficulty in projecting the structure of liquid metals arises because they exhibit duplicity of character as some of their properties are closer to those of crystalline solids and others to fluids. There is an increasing tendency to discuss the structure of liquid metals in terms of the second concept according to which the structure of liquid metals may be conceived as consisting of i) clusters of atoms where the aggregation is a close derivative of that in the crystalline state, ii) individual atoms which behave like true liquids in respect to degrees of freedom and iii) excess number of vacancies. It is noteworthy that the introduction of only 5 pct vacancies is sufficient to transform crystalline matter into the liquid state. At any instant of time thermodynamic equilibrium exists between i, ii, and iii, but the relative proportion of the clusters and random atoms is not known. That this is so can be appreciated by the fact that, when liquid metal is rapidly cooled, liquid state vacancies may condense in the form of dislocation loops and vacancies in excess of their equilibrium number in solid state. These dislocation loops have been observed in thin foils of aluminum prepared from rapid cooled aluminum. As temperature increases above melting point the number and volume fraction of clusters decrease but those of vacancies and random atoms increase. Clusters are transient in nature. In pure metals the cluster is an aggregation of the metal itself. In alloys, however, the nature of the cluster largely depends on the interaction between solvent and solute atoms. If the interaction between unlike atoms is greater than between like atoms: the clusters are then aggregates of unlike atoms. Examples of this kind of system are A1-Cu, Mg-Pb, and so forth, i.e., systems which exhibit negative departures from the Raoult's law. In systems where the interaction between unlike atoms is smaller than be-

Jan 1, 1968

By B. F. Oliver, C. W. Haworth

Pure tin and Sn-0.5pct Pb ingots have been frozen unidirectionally from the base. For quiescent melts that were initially undercooled, a transition from lower eqlciaxed structure to an upper columnar structure is found in the alloy ingots. Columnar to equi-axed back to columnar transitions are observed in superheated alloy ingots, but no such equiaxed band is observed impure tin. The reproducible equiaxed band is associated with a thermal undercooling followed by a recalescence. This undercooling is <5"C, whereas the critical (maximum obtainable) under-cooling for both the pure tin and the alloys used is -20°C. A similar undercooling is observed at the same position in the pure tin ingots, although in this case no clear transition in structure can be seen. The structure of the pure tin ingots is either entirely columnar or mixed columnar-equiaxed. A consideration of the detailed thermal history of the ingots indicates that the ingot macrostructures are determined by the occurrence of a local therlnal undercooling in conjunction with nuclei multiplication and transport mechanisrris. GENERALLY it is found that a pure metal ingot solidifies so as to produce an entirely columnar structure. Frequently an alloy ingot is found to have a columnar outer zone and an equiaxed central portion. Early systematic work to examine the factors controlling the formation of the equiaxed structure was reported by Northcott&apos; who showed that, for copper alloys frozen unidirectionally with a given ingot practice, the alloying element influenced the length of columnar crystals and the extent of the equiaxed structure. Northcott showed that alloys with a wider freezing range more readily produced the equiaxed structure. The nucleation process can be important in producing equiaxed structures; frequently an alloy which readily solidifies with an entirely columnar structure will produce an entirely equiaxed structure when a nucleating agent is added to the melt.&apos; The formation of the equiaxed structure was attributed by Winegard and chalmers3 to the presence of constitutional supercooling; that is, a region of liquid in front of the growing solid could have a temperature below its equilibrium liquidus temperature. Thus, with a small enough temperature gradient in the liquid, it was suggested that the presence of constitutional supercooling may be sufficient to bring about the nuclea-tion necessary for the formation of an equiaxed structure. Although this explanation is plausible, and may be relevant in many ingots, Walker has described an experiment&apos; for which constitutional supercooling seems to be an unlikely cause of nucleation. A Ni-20 pct Cu alloy, repeatedly undercooled more than 50"C, was crystallized and found to show the typical colum-nar-equiaxed structure. The separation between the liquidus and the solidus for the alloy is 40°C. Thus, in this experiment the nucleation required for the formation of the equiaxed structure must have come about in some other way than by the nucleation catalysis constitutional supercooling hypothesis. Chalmers has suggested more recently5 that nuclei (in a typical ingot) are present immediately after pouring and are prevented from redissolving by the constitutional supercooling effect. More recently Uhlman, Seward, Jackson, and ~unt&apos; have shown direct evidence using ice and organic materials that freeze dendritically that the "remelt mechanism" may be an extremely effective crystal multiplication process during the freezing of ingots under conditions involving dendritic growth. JSlia" experimentally demonstrated the detachment of dendrite arms. chernov14 has analyzed the dendrite arm detachment process as a coarsening phenomena driven by the minimization of interphase area. Katta-mis and ~lemings" working with undercooled steel melts give evidence supporting this mechanism. Mechanisms of dendrite arm detachment such as those assisted by convection are believed to be the origin of the macrostructures obtained in this study. This study makes no attempt to distinguish the relative contributions of these mechanisms. The object of the present work was to obtain accurate temperature measurements during the solidification of an ingot and to correlate these measurements with the formation of equiaxed grains in the resulting ingot structures. Similar previous work is very limited. The measurements carried out by Northcott are neither sufficiently extensive nor sufficiently accurate for any interpretation. Plaskett and winegard7 carried out experiments on A1-Mg alloys in which they observed values of the temperature gradient, G, in the liquid and rate of freezing, R (for a given alloy solute content Co), at the transition from a columnar to an equiaxed structure. They reported that equiaxed crystals were produced at values of G/G approximately proportional to the solidus composition. Similar experiments using Pb-Sn alloys carried out by £111011" showed a linear relation between G/R and the solidus composition. However, the thermocouples were in the mold wall rather than in the melt and, in one case, ingot surfaces were examined. There is ambiguity in the meaning of the values of G and R measured in all these experiments. APPARATUS AND EXPERIMENTAL PROCEDURE Alloys were prepared by induction melting 99.999 pct Sn and 99.999 pct Pb to form a Sn-0.5 wt pct Pb alloy in air in a graphite crucible and casting into a cylindrical graphite mold 6 in. long, 1 in. in diarn , and with a & in. wall thickness. This mold was mounted on a copper base through which cooling water could be

Jan 1, 1968

By Donald E. Meyer

High current-low voltage EB-gun evaporation in an oil-free ultra-high vacuum system was found to be necessary, though not sufficient, for stability (300°C, 106 v per on) of aluminium gate MOSFET&apos;s and MOS capacitors not stabilized by a phosphorous glaze. five characteristics of the equipment used: 1) Vacuum purification of the aluminum charge, 2) Ionization of the evaporant by the electron beam, 3) X-ray formation, 4) Residual gases during evaporation, and 5) Metal film structure were studied as Possibly significant in MOS fabrication. EVAPORATION of contact metals common to the semiconductor industry historically has been accomplished with oil diffusion pump systems and various resistance heated evaporant sources as dictated by the type of metal evaporated. To meet a need for greater reliability of semiconductor devices, other metallization methods were developed. A good example would be application of the moly-gold contact system to integrated circuits with deposition by RF or triode sputtering.&apos; More recently, fabrication of stable metal-oxide-silicon devices and circuits has put new demands on metallization. The purity of the thin metal films composing MOS structures is critical, particularly at the metal-oxide interface, and ultra-high vacuum metallization using sputter-ion pumping and electron beam gun (EB-gun) evaporation are well suited for the task. At this laboratory aluminum has been the most common contact-gate metal for both MOS capacitors and MOSFET&apos;s. In the earliest work with MOS capacitors, aluminum was evaporated from wetted tungsten filaments using both diffusion pump and ion pump vacuum systems. In spite of clean oxide techniques these capacitors were unstable under bias-tempera-ture stressing. Only after a switch to EB evaporation of aluminum were stable capacitors produced. Using the same techniques it was possible to make MOSFET&apos;s with equivalent stability. Stability data for a discrete MOSFET is shown in Fig. 1. This is a "clean" oxide gate (no phosphorus stabilization or no etch back of a thicker gate) having a thickness of lOOO? thermally grown on the (111) plane. Gate length after diffusion was 0.24 mils, and the devices were hermetically sealed. Stressing conditions were 300°C and 106 v per cm applied alternately as a positive and negative field for 10 min, 50 min, and 4 hr for a total stress time of 10 hr. An initial shift in turn-on voltage of 0.1 v was detected for 10 min of positive bias. All evidence at this laboratory indicated that while EB-gun evaporation of ultra-high purity aluminum was not sufficient for 300°C stability, it did seem to be necessary. There may well then be something inherent in the EB-gun deposition used which enhanced stability, and probably no single factor existed but rather a series of factors. It is the purpose of this paper to report on some of the investigations carried out to learn more about EB-gun evaporation in ultra-high vacuum systems. EXPERIMENTAL DESCRIPTION The EB-gun was self accelerated, had a maximum power rating of 10 kw, and used a water-cooled copper crucible able to hold a 20-g aluminum charge. The electron beam was bent 180 deg and focused by an electromagnet which also provided movement of the beam across the crucible. Normal power conditions in this work were 9 kv and 300 to 600 mamp. The gun can be described as high-cur rent/low-voltage and was quite different in its mechanism of operation from EB-guns with much higher acceleration potentials. An oil-free vacuum system capable of 5 x 10- l0torr, a quartz crystal rate and thickness monitor and a quadruple mass spectrometer completed the evaporation system, Fig. 2. A typical evaporation cycle consisted of a 3 to 4 hr pumpdown to the upper l0-9 range and evaporation at l0? per sec with the pressure in the bell jar not rising above 1 x 10"7 torr. Thickness control was 5 pct or less and could be automatically monitored and controlled. Five phenomena associated with the EB evaporation and considered as possible contributors to Ma performance included a purification effect, ionization of evaporating aluminum, X-rays, constitution of vacuum ambient during evaporation, and film structure dependence upon evaporation rate. These phenomena are now discussed. Vacuum Purification. The design of the EB-gun permitted purification of the aluminum charge by vacuum outgassing. Particular features included an efficiently water-cooled copper hearth with a capacity of over 20 g of aluminum and the capability for sweeping the beam across the charge. Such capacity meant that aluminum had to be added only after about every fifth evaporation. A new charge was not required each evaporation as is necessary with filament evaporation. An oxide "scum" which appeared on the charge could be completely cleared from the top hemisphere of the charge by sweeping with the beam prior to opening the shutter. An indication of the purifying effect was obtained by a series of analytical measurements on incoming aluminum, after melting but with little vacuum out-gassing, after 30 min outgassing, and the evaporated film itself. Either a solids (spark source) mass spectrometer or an emission spectrometer were used for analyzing the aluminum charge. Analysis of the evapo-

Jan 1, 1970

By F. F. Craig

Many full-scale waterflooding operations are preceded by pilot floods, one purpose of which is to provide an estimate of recoverable oil. A laboratory model study was made to determine the influence of the producing wells&apos; effective productivity on the oil recovery efficiency of single five-spot pilots, as well as single injection well pilot floods. The effective productivity is indicated by the value of Condition Ratio, defined as the actual well productivity to that of on undamaged and non-stimulated, normal-sized well in the same formation. The effects of initial gas satrcration and mubility ratio on recovery eficiency were also investigated in this model study. Model test results skowed that at favorable mobiliry ratios, a five-spot pilot flood can provide a direct quantitative estimate of the recoverable oil in the pilot area. If the pilot producer&apos;s Candition Ratio is 2.2 or more, upwards of 90 per cent of the recoverable oil in the pilot area is recovered from the inside producer, regqrdless of the mobility ratio or initial gas saturation. This Condition Ratio can be achieved with preyent fracturing techniques. Model studies also showed that over the range of imposed injection pressure differences and regional pressure gradients normally encountered in field operations, there was no effect on the recovery efficiency of a five-spot pilot waterflood. Model studies of single injection well pilot waterfloods showed that with no initial gas saturation, the total oil recovery at the offset producing wells can indicate the oil recovery possible by full-scale waterflooding. It is essential that the Condition Ratios of the offset wells be above 1.4. If an initial gas saturation exists prior to water injection, the recoverable oil cannot be directly evaluated by a single injection well pilot flood. However, the production per formance of such a flood can be used to provide information on volumetric sweep efficiency. INTRODUCTION Oil reservoirs are conlplex structures and cannot always be fully studied in the laboratory. Therefore, many operators consider it prudent to evaluate a waterflood prospect by means of a pilot flood. Pilot waterfloods generally involve one of two well arrangements: a single five-spot pilot waterflood, involving four injectors and an internal pilot producing well; and a single injection well pilot flood (sometimes called an inverted five-spot pilot) having one injector and four sur- rounding pilot producers. Some pilot floods are composed of multiple five-spot pilot patterns. To yield information applicable to field-wide performance, the pilot must be located in a representative portion of the reservoir. Pilot floods generally are conducted for one or more of the following reasons: (1) to determine whether water could be injected at desirably high rates, (2) to determine whether an oil bank or zone of increased oil saturation is formed by water injection, and (3) to estimate the oil recovery by waterflooding. Many of the early pilot water-floods were conducted for only the first two reasons. As soon as a buzz in oil production was obtained in the pilot, water injection was initiated throughout the entire lease or field. A number ot laboratory studies have been directed toward determining conditions under which a pilot flood could yield a quantitative estimate of the oil recovery possible by full-scale pattern flooding. One of the early studies of single five-spot pilot flooding&apos; showed that well damage to the inside pilot producer could reduce the total amount of oil recovered. In a study of the single injection well pilot flood pattern,&apos; the results indicated that if the model boundaries were no closer than a half-well spacing beyond the pilot pattern, the pilot performance in the laboratory is unaffected by these boundaries. In another study,? he effect of initial gas saturation and mobility ratio on the ratio of production to injection rate for various groupings of five-spot patterns was defined by mathematical and analog methods. In a study4 involving both potentiometric and flow model experiments at a mobiliry ratio of unity, four different pilot patterns were studied. These included a single five-spot, a single injection well pilot, a cluster of four single injection well pilots and six inverted five-spots. In this study the ratio of well diameter to the distance between injection and producing wells was held constant at 1:1000. The effect of the 7 ratio-—the ratio of the pressure drawdown at the producing wells to the pressure build-up at the injection wells on the pilot performance-was studied. The values of 7 ratio ranged from 0 to 0.34. Results showed that both the total oil recovery and the total fluid production from the pilot relative to the cumulative injection increased with increasing values of the 7 ratio. The effect of both the ratio of injection to producing rates and mobility ratio on the oil recovery performance of a liquid-saturated single five-spot pilot flood was studied in a series of flow model tests.5 Rate ratios ranged from one to four, and mobility rates ranged from 0.1 to 10. Resulls of these tests showed that at low rate ratios, the pilot producers may recover up to four times the recover-

Jan 1, 1966

By Leonard B. Gulbransen, John R. Lewis, W. Martin Fassell, J. Hugh Hamilton

T. E. Leontis (The Dow Chemical Co., Midland, Mich.)—This paper is of particular interest to me because of my own work with F. N. Rhines on the oxidation of magnesium and magnesium alloys a few years ago. The authors are to be complimented on their development of an accurate and reproducible technique for measuring ignition temperatures and on their comprehensive study of the many variables that affect the ignition temperature of magnesium. It is indeed gratifying to see that they have obtained a good correlation between ignition temperatures and the oxidation rates reported by us. The correlation is valid not only with composition within one alloy system but also between alloy systems; that is, alloying elements which effect the greatest increase in oxidation rate also produce the greatest decrease in ignition temperature. There are a few points upon which I would like to comment. In attempting to correlate ignition-temperature data, one must be sure that the same definition of this quantity is used by all investigators. It does not appear to me that such is the case in the authors&apos; comparison of their data with the theoretically calculated values of Eyring and Zwolinski. The equation derived by these investigators defines the ignition temperature, To, as the temperature at the gadoxide interface, whereas the present authors use the metal temperature as the criterion for ignition. The contradiction in the effect of oxide-scale thickness on ignition temperature between the predictions of the Eyring-Zwolinski equation and the observations reported in this paper indicate that some variable has not been taken into consideration. Could that be the geometry and size of the specimen? There is a marked difference in the type of specimen used in this investigation and that used in our work which formed the basis of Eyring and Zwol-inski&apos;s theoretical treatment. Another factor which plays an important role in ignition is the vapor pressure or the rate of vaporization. Combustion can safely be assumed to take place in the vapor phase by the reaction between vaporized magnesium and oxygen. Thus, a more accurate theoretical analysis may be made on the basis of the rate of vaporization which may be the controlling rate of the process. The effect of a large number of alloying elements on the ignition temperature has been reported in this paper, but beryllium was not included. Practical experience dictates that beryllium markedly decreases the burning tendency of magnesium. I was wondering if the authors plan to study the effect of beryllium in their future work. The authors predict that concentrations of sulphur dioxide in the furnace atmosphere greater than 5.8 pct would be expected to increase the ignition temperature to values still higher than those they measured. I would like to mention that large concentrations of sulphur dioxide markedly increase the rate of combustion of magnesium once ignition has started. Although it has been shown in the paper that the ignition temperature of magnesium in oxygen increases with increasing sulphur dioxide content up to about 1 to 2 pct, in practice relatively low-melting commercial cast alloys (AZ63A and AZ92A) are being continuously heat treated at temperatures just below the melting point in air containing 0.5 to 0.75 pct SO*. In regard to the change in color of the oxide scale observed on magnesium and magnesium alloys just prior to ignition, I would like to mention that in our work alloying elements were found to color the usually white magnesium oxide even though ignition did not occur. For example, the oxide formed on Mg-A1 alloys was gray, increasing in intensity with aluminum content in the alloy. Finally, I might suggest that the authors indicate their source of the value of 0.8 g per cc for the density of MgO as it is formed on magnesium upon oxidation at elevated temperatures. W. M. Fassell, Jr. (authors&apos; reply)—The comments by Dr. Leontis are very excellent ones and I will attempt to answer them in order. First, the problem of ignition of magnesium is a rather difficult one since many factors are involved. Concerning the comparison of the To in the Eyring-Zwolinski equation, eq 4, with the experimentally determined values, it will be noted that the calculated and experimental values of the ignition temperature in Table I are not self-consistent. In the case of the 1.78 pct A1-Mg alloy the calculated value is 49°C below the experimental value; for the 3.81 pct A1-Mg alloy, 122°C below the experimental value; for Mg with 5x10-&apos; cm film, 19°C above the experimental value; for Mg with 2x10-I cm film, 28 °C below the experimental value. Thus, if it were merely a matter of difference of location of temperature measurement the calculated ignition temperature would always be below the experimental value, the difference being due to the thermal gradient through the oxide film. The possibility of a thermal gradient in the magnesium metal must be considered. From Carslaw and Jaeger,&apos;Y t can be shown that the maximum temperature gradient that could exist between the oxide-metal interface and the center of the sample is of the order of O.Ol°C. The geometry and size of the specimen could certainly have some effect on the ignition temperature. The equation for ignition that has been proposed in reference 14 is of the following type containing terms to account for this and other factors: M dT AHv(T) =Cp--------------\-J(.T—TB) + ZAHl-M A dx where AH is the heat of reaction, v(T) is the velocity of the reaction at temperature, Cp is the heat capacity of sample, M is the mass of sample, A is the area of sample, t is time, J is the total coefficient of heat transfer outward from the reaction zone, TR is the temperature of the bath or furnace, and AH,, is the heat associated with any phase change involved. Prior to the instant of ignition, the vapor pressure of magnesium is of no special significance. After ignition, neither eq 4 nor the above equation is applicable. The actual combination of magnesium cannot safely be assumed to take place in the vapor phase. While experimental data is lacking to support a hypothesis that ignition does or does not occur in the vapor phase, some observation on the pressure ignition experiments may be of interest. At high oxygen pressures, once ignition has occurred, the reaction of magnesium with oxygen approaches near explosive violence, the entire sample being consumed in probably less than 1 sec. At atmospheric pressure it usually requires 15 to 20 sec. Thus it appears that the oxygen concentration becomes the rate determining factor. Further, if burning magnesium is observed through darkened glass (Lincoln Super-visibility Shade No. 12) the magnesium sample is very much hotter than the "smoke" and the outline of the sample is retained perfectly. No "flame" is visible above the metal. No work was done on Mg-Be alloys. We do, however, intend to study this problem in the near future.

Jan 1, 1952

Joseph LeConte, Berkeley, Gal.: I have read with some care and with extreme interest the work of Dr. Don, and have 110 hesitancy in expressing my high estimate of its value. We have here an example of laborious work undertaken in the true scientific spirit and by right methods. Loose statements and rash conjectures are here brought to the test of chemical analyses. By such work only may we hope to reach reliable conclusions and finally to solve the complex problems presented by the occurrence of ore-deposits. Such work as this is not only scientific but Is in the highest degree practical; for while a crude and imperfect science, by interfering with the results of approved empirical methods, may be positively hurtful, a more perfect science must eventually become the only sure guide to practice. Such a more perfeet science can only be reached by such work as Dr. Don&apos;s. I am sure every member of the Institute will unite with me in the hope that Dr. Don will continue his work, and that his example will incite others to similar work. S. F. Emmons, Washington, D. C.: I desire to bear my humble testimony to the great value of Dr. Don&apos;s paper to the science of ore-deposits, the thoroughness and accuracy of his work, and the immense amount of care-taking and tedious labor which it represents. The only regret with regard to it is that it could not have been published in full. No more important paper in its line has ever appeared in the Transactions. Indeed,

Jan 1, 1898

By Hugh H. Waesche

AN adequate supply of crystalline quartz of piezoelectric grade and size continues to be of fundamental importance to the U. S. Army Signal Corps. Current electronic development programs of the Armed Forces depend upon the use of quartz crystals in all applications where accurate frequency control is necessary. In peacetime this&apos; may not seem too significant, but in planning for possible national defense emergencies, an adequate supply of piezoelectric grade raw quartz is just as important as an adequate supply of some of the more publicized strategic minerals. Prior to World War II, the Signal Corps accepted the use of quartz crystals for frequency-control purposes in essentially all electronic communication, navigation, and radar equipment operating in the audio and radio frequency spectra up to and including the ultra-high-frequency channels. Over 4,000; 000 lb of radio-grade quartz was required between January 1942 and V.J Day. Use of such a large quantity of crystal units was necessary in order to establish and maintain, with a minimum of effort, clear and definite frequency channels of greater stability than could be obtained by any other means. This policy was justified on the basis that quartz was without a peer as a frequency-controlling element. Military and civilian uses of quartz in the field, as well as laboratory studies, have confirmed this premise and no means of highly stable frequency control, superior to quartz, has been discovered. It appears certain that the demand for use of quartz for frequency control purposes will continue at a high level.

Jan 1, 1948

By AIME AIME

ABOUT one hundred were in attendance when Donald M. Liddell opened the session* on non-ferrous metallurgy at 2 p. m. on Tuesday. F. F. Col- cord was vice-chairman. For the first part of the session the chair was turned over to Frank G. Breyer, who introduced G. L. Spencer, Jr., to read his contribution (T.P. 378), "High Silica Retorts at the Rose Lake Smelter," which was an account of the method of manufacture of high-silica zinc retorts at the Rose Lake smelter, and of the service given by these retorts. The materials used are, by volume, 50 per cent clay, 25 per cent silica flour and 25 per cent grog. Written discussion of the paper by E. M. Johnson, W. R. In- galls and M. M. Neale was read by Mr. Breyer. Mr. Johnson explained that their practice in manufacture differed very little from Rose Lake practice, but that their retorts did not last as long, possibly because Eagle-Picher does not use a hydraulic retort press or sintered ore. He ascribes the longer life of silica re- torts to the fact that they do not bend under heat. Mr. Ingalls pointed out that silica retorts are no better as heat conductors than clay retorts, but that they do have a superior rigidity in the furnace. The character of the retorts does not affect the density of the charge. Mr. Neale gave the procedure in the manufacture and use of high-silica retorts at the Donora zinc works, not

Jan 1, 1931

By G. F. Loughlin

THE matter of grading Indiana oolitic limestone has been under a cooperative study by the Supervising Architect&apos;s office, the U. S. Geological Survey, the Bureau of Standards, and the former Indiana Limestone Quarrymen&apos;s Association. As the criteria for grading are necessarily based on a number of geologic and related factors of which those quarrying and using the stone had only imperfect appreciation, the first part of the report is a very elementary account of the origin, structure, and the chemical and physical properties of tie stone, and their relations to durability and utilization, and serves as a foundation for the second part, which discusses grading and pro- poses limits for grades established by the quamymen. Salient features of Part I of a report that has been prepared are the variations in uniformity of stone due to cross bedding, and local uncomformities; the relative prominence of weathering effects on the coarser uneven grained surfaces, and its apparent absence on fine, uniform grained surfaces, although the amount of weathering is the same on each; the attributing "crow feet" (stylolites) to solution under pressure, and the explanation that, whereas the thinnest "crow feet" have no noteworthy effect on weathering quality or strength, the thicker ones are likely to weather out rapidly and to promote splitting; the influence of fracturing on the oxidation of the original gray or "blue" to buff color above the ground water level; the interpretation of chemical analyses and the pointing out that both the gray and buff colors are due mainly to organic

Jan 1, 1929