Search Documents

By A. W. D. Hills

This paper describes the development of a generalized integral-Wofile method for the analysis of heat transfer dwing solidification. The method is extremely flexible, and can be applied to a wide range of situations. This flexibility has been achieved by characterizing the solid metal layer in terms of two parameters, and by developing two simultaneous nonlinear differential equations for these parameters in terms of the heat fluxes crossing the boundaries of the solid layer. The use of these equations is illustrated in a series of examples which involve the solidification of pure metals at zero superheat cooling under different conditions. The simplicity with which the method can be extended to treat more complicated jwoblems is illustrated in a further example which involves natwal convection effects in the liquid metal. ThE rate at which molten metal solidifies in an industrial casting process, and the structure of the cast product, are both controlled by the rate at which heat can be removed from the casting. A knowledge of heat transfer rates is thus essential to the control of the process and to the control of the structure and soundness of the final casting. Heat transfer rates during real solidification processes cannot be predicted by formal mathematical techniques, however, because nonlinear boundary conditions are involved. Approximate methods are normally used, and these have included electrical and hydraulic analogue techniques, finite difference methods, and the integral-profile method. Considerable effort has been devoted to the development of the first two techniques, but the integral-profile method has been used very little so far. This is unfortunate because the method is capable of providing relatively accurate solutions for the heat transfer equation during solidification without involving large amounts of computer time. A further advantage of the method is its flexibility, although this is not apparent from the integral-profile solutions that have been developed to date. These solutions have been derived for the solidification of molten metal at zero super-heat under cooling conditions involving either a constant heat flux from the cooled surface;' a constant heat transfer coefficient at the surface,'-3 or a specified variation in the surface temperature.4,5 A generalized integral-profile method is presented in this paper which can be used to predict unidirectional solidification rates under a very wide range of more realistic cooling conditions. The use of the method is illustrated in a series of problems involving pure metals, or skin forming alloys, solidifying at zero super-heat. However, the principal advantage that this method has over the previous integral-profile methods is the ease with which it can be extended to treat more complicated solidification problems. This is illustrated by considering a problem in which super-heat is liberated from the liquid metal by natural convection during the solidification process. In the final section of the paper the generalized method is compared with previous methods used to predict solidification rates and its extension to more complicated solidification problems is briefly discussed.

Jan 1, 1970

By J. B. Dyess, H. A. Miley

Tarnish films on some of the common metals (particularly on copper and silver) have been of much scientific and commercial concern for a long time, but before the development of the electrical method1 of measuring film thicknesses there was no satisfactory quantitative approach by which to study the separate parts of these complex films. This method has been adapted to the measurement of duplex (cuprous-cupric) oxide films on copper.2 In the present work it has been used to measure tarnish films on copper when they were mixtures of cuprous oxide and cuprous sulphide, and also when they contained cuprous oxide, cupric oxide and cuprous sulphide, each component part being measured at a different potential value. Oxide-coated copper specimens, prepared by heating copper in air at chosen temperatures for given periods, were exposed to moist hydrogen sulphide in air to forml the various oxide-sulphide films studied. The comparative resistances afforded by (I) different thicknesses of oxide films, and also (2) equal thicknesses of oxide and sulphide films, against severe attacks of hydrogen sulphide were measured. The electrical method requires that the time be observed for the cathodic reduction of each part of the film substance, and these respective time values multiplied by the constant current give the corresponding quantities of electricity expended. Then each millicoulomb per square centimeter represents a film thickness of M X 108____ 2DX 96,494 X 103 where M is weight of oxide (or sulphide) giving one gram-atom of oxygen (or sulphur) for cathodic reduction, D is density of the oxide (or sulphide) and t is the thickness in Angstrom units per millicoulomb per square centimeter. The value of t for cuprous sulphide (cubical) is 14.27, and is obtained by substituting 5.78 for D and 159.20 for M in equation a. Previous values hf t for cuprous and cupric oxides (12.36 and 6.39, respectively) were used in the present work.

Jan 1, 1939

By J. B. Dyess, H. A. Miley

Tarnish films on some of the common metals (particularly on copper and silver) have been of much scientific and commercial concern for a long time, but before the development of the electrical method1 of measuring film thicknesses there was no satisfactory quantitative approach by which to study the separate parts of these complex films. This method has been adapted to the measurement of duplex (cuprous-cupric) oxide films on copper.2 In the present work it has been used to measure tarnish films on copper when they were mixtures of cuprous oxide and cuprous sulphide, and also when they contained cuprous oxide, cupric oxide and cuprous sulphide, each component part being measured at a different potential value. Oxide-coated copper specimens, prepared by heating copper in air at chosen temperatures for given periods, were exposed to moist hydrogen sulphide in air to forml the various oxide-sulphide films studied. The comparative resistances afforded by (I) different thicknesses of oxide films, and also (2) equal thicknesses of oxide and sulphide films, against severe attacks of hydrogen sulphide were measured. The electrical method requires that the time be observed for the cathodic reduction of each part of the film substance, and these respective time values multiplied by the constant current give the corresponding quantities of electricity expended. Then each millicoulomb per square centimeter represents a film thickness of M X 108____ 2DX 96,494 X 103 where M is weight of oxide (or sulphide) giving one gram-atom of oxygen (or sulphur) for cathodic reduction, D is density of the oxide (or sulphide) and t is the thickness in Angstrom units per millicoulomb per square centimeter. The value of t for cuprous sulphide (cubical) is 14.27, and is obtained by substituting 5.78 for D and 159.20 for M in equation a. Previous values hf t for cuprous and cupric oxides (12.36 and 6.39, respectively) were used in the present work.

Jan 1, 1939

Manganese deposits discovered in Maine may solve one of the problems facing the steel industry today. Diamond drilling is scheduled to start in Aroostook County to determine whether the ore is of acceptable grade. The Bureau of Mines estimates the deposit contains several hundred million tons. If true, it means about a 30-year supply. The steel industry presently imports about 90 pct of its needs. Noranda Mines, Ltd., is planning a sulphur-iron plent for Ontario's Niagara Peninsula. Although contracts have not been signed, a substantial agreement has been reached with American Cyanamid, Ltd., whereby the Noranda plant would be constructed adjacent to Cyanamid's chemical plant at an estimated cost of million. The unit would treat approximately 100,000 tons of pyrite concentrate annually. San Manuel Copper Corp., wholly-owned subsidiary of Magma Copper Co., is asking the RFC for a $111.28 million loan for development of a copper orebody in Pinal County, Ariz. The property s said to be capable of producing 10 million tons of ore annually. San Manuel plans to construct facilities for processing 30,000 tons of ore and for smelting 800 tons of concentrate daily. An Aeromagnetic map covering 120 sq miles of the Wichita Mountain area in southwestern Oklahoma indicates a possibility of iron production from titaniferous magnetite deposits of the Raggedy Mountains, northwest of Lawton. The map shows an area in the north central part of the region which may prove favorable to further development.

Jan 1, 1952

By Robert E. Hochscheid

The subject article appears in the February, 1978, edition of Mining Engineering, and on page 190 carries the statement, "As most operators know, in a Water-Only cyclone, ability to adjust the vortex finder is quite important due to the sensitivity of this type of operations to variance in feed conditions and having to take them apart to make this adjustment is always a nuisance." Our experience as a manufacturer and supplier of Water Only cyclones does not agree with the above statement, and we offer the following brief discussion. Our company finds that the sensitivity of the Water-Only cyclone is a function of the fineness of the coal being washed, with the sensitivity to vortex finder length being greatest for coals coarser than 3/4-in. and virtually insensitive to raw coal finer than 1 mm. For coals finer than 1 mm, we find that we can use the shortest standard vortex finder in either our 10- or 15- in. Water Only cyclone without exception. For coals 5/8-in. x 1 mm ceramic vortex finders of fixed length have been satisfactory in all cases following an initial testing period in which the length was determined. Coals coarser that 5/8-in. are more sensitive to the vortex finder length, and two installations handling coals coarser than 1-in. continued to experiment with vortex finders of various lengths long after the initial startup period. For coals of all sizes, final adjustment of product quality has been achieved by determining the optimum size of apex orifice, which is accessible and readily changed, if necessary. Comments above assume no unusual change in the coal being washed or the required quality of clean coal.

Jan 1, 1979

By Francis Flynn

MANY excellent papers, descriptive of the milling and smelting of every kind of commercial ores, the refining of virgin metals, the casting into various shapes demanded by the trade, the rolling into shapes best suited to the factory machinery and the making of composition alloys to suit every requirement have been issued by the many technical societies dealing with non-ferrous metals. It is a wonderful collection of papers, of which the mining and metallurgical engineers may well be proud, but strange as it may seem, metallurgists in general appear to take the stand that when they have delivered suitable alloys to the foundry and rolled products to the factory their duty to write papers has ceased, at least in so far as the A. I. M. E. is concerned. Still we read in the daily papers that the mining companies are absorbing metal-manufacturing industries. The purpose of this paper is to describe the reclaiming of non-ferrous scrap metals at manufacturing plants, taking as an example the automobile industry.

Jan 1, 1929

By E. P. Mathewson

W. W. (Pop) Adams' contribution is short and to the point. "I went to Pueblo about March, 1881, and started working for the Pueblo Smelting & Refining Co. in the sampling room, going from there to the assay and chemical departments, and ending in charge of the lead refinery on the night shift. I was there about two years, returning to California in 1883. The plant was under the management of Mather and Geist, plus Charley Ballard; Herman Schlapp was the metallurgist. Herman Schlapp's name remains prominently in my recollection of Pueblo for his never-failing kindness and charity to the young men who were trying to learn the Pb. game. John Allen, Walter Koehler, George Westcott, Charley Molson, and Alfred de Ropp were there with me. Schlapp and Koehler I have never seen since I left Pueblo; the others I have met often. , Alfred de Ropp I have often met-here, as he was manager of the Selby Smelting & Lead Co. of San Francisco, for years. 'He tells me that I gave him the rudiments. of American profanity at Pueblo; an apt pupil, for since then, by his own efforts, he has added largely to his vocabulary..

Jan 12, 1923

PRESIDENT ROBERT E. TALLY, JEROME, ARIZ. PAST PRESIDENTS FREDERICK W. BRADLEY, SAN FRANCISCO, CAL. WILLIAM H. BASSETT, WATERBURY, CONN. TREASURER KARL EILERS, NEW YORK, N. Y.

Jan 1, 1923

By C. S. Smith

QUANTITATIVE methods were used to good effect in the earliest days of metallography1-3 but they mysteriously passed into virtual disuse until the important paper4 by Howard and Cohen in 1947. Various devices for the measurements of integrated linear intercepts have been constructed, primarily by petrographers. The hydraulically operated stage designed by the writer5 was satisfactory, but prolonged use caused air bubbles to become entrapped, which introduced back-lash. A new stage has been constructed which avoids this defect and provides better integration when measuring directional structures. This utilizes a circular traverse, and integration is achieved by counting electrical pulses produced by a photocell and a light chopper.* The stage is shown diagramatically in Fig. 1 and in photograph, Fig. 2. It is of simple construction. Mounted on a plate with clamps to fit the stage of a standard metallurgical microscope is a worm and 100-tooth worm gear, the latter supporting the specimen to be measured. The worm is manually actuated by a knob which contains inside it three

Jan 1, 1961

By R. Schempp

DURING the past few years, general interest in the steel-producing and steel-consuming industries has been centered on the so-called "inherent characteristics" of steels. While often vaguely described, these char-acteristics are known to influence the response to heat-treatment and the hardening characteristics of the material. Although most of the recent papers and discussions have associated the "inherent characteristics" with the austenitic grain size and empha-sized the importance of it, comparatively little is known of the variables that may affect the size of the austenite grain. The work to be described in this paper was carried out during the course of a study on the inherent characteristics of tool steel containing one per cent cart on. The discrepancies encountered in the determination and classification of the austenitic grain size led to in investigation of some of the variants influencing the austenitic grain size as determined by standard methods.

Jan 1, 1937

By Warren Smith

IT has been 5 years since the writer left the Philippine Islands and while in that country his chief work did not lie in this field, though he has visited all but one of the localities mentioned in this article. The principal field studies relating to oil were made by his colleague, Mr. Wallace E. Pratt. The writer's investigations dealt with the general stratigraphy and paleontology of the Philippines. With the exception of the investigations made by Mr. Pratt and the writer very little information on this subject is available. A number of geologists in the employ of large oil companies have visited the Islands from time to time but, following the general rule, the public has scarcely ever been permitted to learn anything of the results. The writer is indebted to the Bureau of Insular Affairs, Washington, for late information regarding recent legislation in the Islands relating to petroleum. All the known oil seeps, petroleum residues, such as ozocerite, and natural-gas emanations are associated with Tertiary sediments. The chief seeps and most promising prospects are located as follows: 1. Bondoc Peninsula (lower end), Tayabas Province, Southeast Luzon. 2. The west coast of the island of Cebú from Alegria north to, and perhaps beyond, Toledo. 3. Central Mindanao not far from Lake Lanao. 4. The ozocerite veins on the Island of Leyte in the northwestern part in the vicinity of the town of Villaba. 5. Natural gas from some deep wells in Tertiary shale formations on the eastern flank of the Cordillera and extending out under the plain on the island of Panay.

Jan 2, 1920

By J. C. Yannopoulos, N. J. Themelis

Ah electronic thermogravirnetric balance was used to measure the veductioiz rule o single cirpric oxide particles suspended in a stream of hydrogen. Very jzne thermocouples embedded in lie center and at the surface of the sphere recorded the variation of terw perature during reduction. In contrast to iron oxide reduction, where in most instances the rate of interface reactiokl is controlling, the heat- and mass-transfer phenotnena play a predolrinant role in the reduction of cupric oxide. The correlation of experitnental data or tnass lransfev lhrough the boundary layer at Reynolds nunlber 0-4 50 was as jollocs: ThE reduction of cupric oxide by hydrogen is represented by the equation: It is a highly exothermic reaction and the amount of heat released varies only slightly with temperature (-21,430 cal per g-mole at 400°C). Most of the published studies on this system have been conducted at temperatures in the range of 34 to 280c.l-&apos; The concensus of opinion has been that at temperatures below 200°C the reaction is preceded by an induction period during which there is very little or no reduction. The length of this period diminishes as the temperature of the reaction is increased1l5 and aseawa found that at 280°C reduction starts practically immediately when the oxide is exposed to hydrogen gas. The existence of an induction, or incubation, period has led experimenters to believe that the reduction of CuO by hydrogen is catalyzed by metallic copper.&apos; Boldurev and rmolaev found that mechanical additions of powdered copper to oxide did not affect its reduction, although metallic copper produced during the reduction seemed to have a catalytic effect. At least three other authors2&apos;5&apos;7 have reported that addition of copper had no effect on the rate of reduction. Pease and alor&apos; observed that water vapor had a strong inhibiting effect on the reduction at 1503C, but its effect was greatly diminished at 200 C. Pavlychenko and Rubinchik5 studied this reaction at 159 to 235 C and found that, once the reaction had been initiated, there was no inhibiting effect due to the introduction of water in the hydrogen stream; at temperatures above 183°C there was no inhibiting effect due to water vapor, either before or during reaction. The same authors noted that the rate of reduction was independent of pressure in the range of 200 to 700 mm Hg. aseawa investigated the kinetics of the CuO-Hz system at 160 to 280°C and estimated the apparent activation energy at 14,000 cal per g-mole. A similar value (13,500 1200 cal per g-mole) was reported by ond&apos; in the temperature range 148 to 216°C. Bond also reported that there was no incubation period and that water vapor had no inhibiting effect on reduction at temperatures above 190 C. The above studies have been conducted at temperatures below 280°C and the physical configuration of the system under investigation has not been defined adequately. However, it is well-known that the mechanism of gas-solid reactions depends on a number of in series physical and chemical rate prcesses.&apos;&apos; It is, therefore, essential to include among the experimental factors the geometry of the solid system and the mass-transport characteristics of the reducing gas. Scott studied the reduction of packed beds of cupric oxide cylinders by Hz-He streams of very low hydrogen concentrations at temperatures 400 to 600 C, pressure of 10 to 30 atm, and gas velocity from 0.18 to 5.8 ft per sec (3 < Rep < 30). The reduction rate was found to be mainly controlled by diffusion through the boundary layer and through the pores of the reduced copper phase. The following correlation was proposed: Scott in an earlier work studied the reduction of fixed beds of cupric oxide wire and found that the rate of flow of the gas stream through the bed had a controlling effect on the rate of reduction. The same mass-transfer phenomenon was observed by Bond and clark13 on a similar reduction system. The analogy between mass and heat transfer through the boundary layer which exists between a solid surface and the bulk stream stems from the similarity of the differential equations representing these phenomena

Jan 1, 1967

By C. J. Frosch, J. A. May, H. G. White, C. D. Thurmond

Gallium phosphide epitaxial layers were grown from the vapor phase on undoped single-crystal galliurn arsenide substrates in silica tubes by an open-tube wet-hydrogen process. The epitaxial layers were grown over a range of water pressures at three substrate temperatures. Excess donor concentrations were determined by surface barvier capacitance measurelrzents without removing the layers from the substrates. The excess dmlor concentration, ND-NA, is fo~ind to vary approxilnately inversely with the pressure of water added to the hydrogen carrier gas. This is the relationship that would be expected for singly ionized silicon donors on gallium sites in extrinsic galliunz phosphide, with the silicon coming from the SiO generated by the reaction of hydrogen with the silica tube. An increase in the partial pressure of water in the hydrogen stream decreases the SiO pressure. The results indicate that ni, the intrinsic hole and electrmt concentration for gallium phosphide at the three substrate temperatures, is smaller than the concentration estimated from available data for the density of states effective masses and the energy gap. Mass-spectrographic measurements confirm that the dono?, introduced into gallium phosphide is silicon. The equilibrium concentrations of silicon in vapor-flown gallium Phosphide have been estimated from available thernzodynamic information that includes the solubility measurements of silicon in gallium phosphide in equilibrium with a gallium-rich liquid phase. Satisfactory agreement with the measured silicon concentrations is obtained. FROSCH1 has described an open-tube process for growing single-crystal Gap from the vapor phase by a GazO transport mechanism. The method depends upon the reaction of H20 in an H2 carrier gas with a heated source of polycrystalline Gap which provides the necessary vapor species. When the temperature of these vapor species is lowered, super saturation occurs and single-crystal Gap will deposit on a suitable substrate. Unintentionally doped single crystals of Gap grown by the wet H2 process in silica tubes are n type. Evidence is presented to show that the donor introduced is silicon, and that a qua si-equilibrium model accounts for the inverse dependence of the donor concentration on the water partial pressure and predicts the magnitude of the donor concentrations. Ainslie et al. experimentally showed a similar inverse relationship between the carrier density and oxygen pressure for GaAs. Emission-spectrographic analyses showed a decrease in the silicon concentration with increasing oxygen overpressure for GaAs. Cochran and Foster suggested the theoretical possibility of suppressing silicon contamination by using Ga20 generated by the reaction of gallium with water vapor. 1) EXPERIMENTAL The apparatus and procedures are essentially the same as those described by Frosch.&apos; The apparatus consists of a 25-mm-ID SiO2 tube extending through a controlled high-temperature flat zone for the location of the polycrystalline Gap source and a downstream temperature gradient falling at a rate of about 14°C per cm. The latter provides the region of super saturation for the location of the single-crystal substrate. The partial pressure of water in the inflowing hydrogen stream, pA2, O was controlled by mixing me-tered proportions of dry H2 with H2 saturated with H2O vapor at 0°C. The total gas flows were about 200 cu cm per min in all experiments. The Gap sources were prepared by pulverizing boat-grown polycrystalline ingots to pass a 20-mesh sieve. The substrates were cut from an undoped single-crystal boat-grown GaAs ingot purchased from Monsanto. This ingot had a carrier concentration of about 1015 atoms per cu cm, a resistivity of about 5 ohm-cm, and a mobility of about 5000 sq cm per v sec at 25°C. Substrates with dimensions of 1 by 1 by 5 x lo-&apos; cm were employed. The growth faces were chemically polished (111) arsenic faces. Epitaxial layers, at least 7.5 x 10-3 cm thick, were grown,. This required from 1 to 24 hr depending upon the Pii2Q values and the temperatures. In all of the runs, the source temperatures were 50°C higher than the substrate temperatures. Samples were prepared

Jan 1, 1968

By DR. DOUGLAS

Discussion of the Paper of Dr. Douglas, presented at the Toronto Meeting of the Institute, July, 1907 (Trans., xxxviii., 455 to 471). EDGAR HALL, Silverspur, Queensland, Australia (communication to the Secretary*) :-Dr. Douglas has written on this subject before, and his influence has had a powerful effect on the side of freedom among the younger generation of engineers. Moreover, it is not the first time that he has attributed the decline of the copper-smelting industry in Swansea to the secrecy maintained by the firms there engaged in smelting-operations. In this latter statement I think his conclusions are open to criticism. Whether the firms referred to have suffered by their secrecy is their own business-I. bold no brief for them ; but that the decline of the copper-industry at Swansea was inevitable seems to me to be proved conclusively by Dr. Douglas&apos;s own writings. In his paper on The Copper Situation,1 Dr. Douglas says "In comparing iron and copper mining, . . . it must be remembered that 2 tons of average iron ore from the most prolific source now available will make 1 ton of metal; whereas from 33 to 75 tons (say an average of 50 tons) of copper ore must be mined to produce 1 ton of copper." And further: "Last year&apos;s production of iron was made from approximately 50,000,000 tons of ore. Our copper mines, to yield a production of 900,000,000 pounds, must have handled approximately 22,000,000 tons of ore, or nearly half the quantity raised from our iron mines." Is not this the key to the whole situation ? In transporting the 50,000,000 tons of iron-ore, 25,000,000 tons of the metal iron were carried so much nearer to the market, but the transportation of 22,000,000 tons of copper-ore would have carried only 450,000 tons of the metal copper nearer to its ultimate destination. The small percentage of copper available in its ores makes

Sep 1, 1908

THE Fall Regional Meeting of the Institute, which has now for some years been held in cooperation with the Western Division of the American Mining Congress, will be held this year at Joplin, Mo., in the heart of the great Tri-State district. This year the Tri-State Zinc and Lead Ore Producers Association is joining in the meeting. The Society of Economic Geologists will also take part though not offering any papers. The district in which the meeting is held includes adjacent parts of Missouri, Kansas and Oklahoma. Out in the heart of a fertile prairie farming country, it is one of the major mining districts of the world. It produces normally approximately one-third of the zinc ore mined in the United States which is equivalent to nearly one-half the zinc since the concentrate has always been notable for the height of its grade. Even in the depressed business year 1930, the American Bureau of Metal Statistics credits the district with 434,460 tons of concentrates equal to 217,230 tons of zinc out of 1,503,095 and 576,630 respectively for the country as a whole. This was equal to about one-seventh of the world&apos;s output of zinc, more than that of any foreign country. In addition about 75,000 to 100,000 tons of lead is annually furnished by the same mines. Elsewhere we present a general description of the district prepared for this meeting by J. C. Heilman, a Lehigh graduate, who has spent the past eleven years there and has had charge of explorations for many of the companies.

Jan 1, 1931

By Fred C., Fred C. Bond

Comminution energy is principally energy of deformation before breakage, which appears as heat. An empirical equation is presented which covers the entire comminution range. The new strain-energy theory considers comminution from the known principles of mechanics and the reduction ratio. Energy requirements according to the different theories are compared.

Jan 1, 1950

By Charles L. Thomas

A novel, highly sensitive, and reproducible nzetlzod for the determination of hydrogen in solid materials is presented. The procedure requires equilibration of the specimen with hydrogen gas, rapid quenching, and hot vacuum extraction of the dissolved gas with subse-quent quantitative analysis by mass spectroscopy. Good linearity is obtained for the Arrl~enius plots of the investigated metals. The advantages in the use of this method over that of Sieverts aye discussed. The solubility data for copper are in reasonable agveewzent with a considerable number of other inuestigations, wllile those fov silver are considerably lower than previously reported. The first known solubility data for gold are presented. Solubility equations and heats of MUCH of the data which are available on the solubility of hydrogen in various metals and alloys have been obtained by the classical Sieverts method.&apos; The method involves the measurement of a decrease in pressure of a gas in a calibrated system, and the calculated contraction in volume is attributed to the solubility of the gas in the metal sample. The procedure requires several corrections, such as the solubility of the gas in the container walls and the diffusion of the gas through these walls, as noted by Steacie and .Johnson2 and others. In addition, errors may be incurred due to reactions between metal surface impurities, such as oxides, and the saturating gas. The precise calibration of the measuring system where large thermal gradients exist can present additional difficulties. Also, accurate volumetric measurements of small quantities of gas are difficult. Many of the objections to the Sieverts method were overcome on solid materials by Ransley and ~eufeld,~ who first saturated the metal with hydrogen and performed a subsequent extraction and measurement of the gas by chemical means. Eichenauer and pebler4 and Eichenauer, Kiinzig, and pebler5 measured the diffusion coefficient and solubility by following the degasification of a sample as a function of a rate of increase in pressure in a previously evacuated system. Here again, however, the procedure involves many of the corrections of the Sie-verts method. The present investigation deals with the solubility of hydrogen in solid copper, silver, and gold by a technique which eliminates many of the aforementioned corrections and possible errors. This procedure requires equilibration of the specimen with gas, rapid quenching, and hot vacuum extraction of the dissolved gas with subsequent quantitative analysis by mass spectroscopy. EXPERIMENTAL Two completely separate systems were employed to accomplish first, the equilibrium saturation of the sample and second, the extraction of the dissolved gas. Saturation Apparatus. The saturation apparatus, illustrated in Fig. l, consisted of a vertically mounted quartz tube with a three-way valve for vacuum or hydrogen near the top and an outlet near the bottom leading to a butyl phthalate seal. The bottom end of the tube was terminated with a joint accommodating an O-ring sealed "Asco Stirring Gland" (The Emil Greiner Co.). This gland facilitated movement of the thermocouple without introduction of air into the system. The upper portion of the tube (above the furnace) was water-jacketed. A Welsh 1405-B mechanical pump provided the necessary system evacu-

Jan 1, 1968

By R. W. Gurry

Thermodynamic calculations indicate that boron is a better deoxidizer than silicon but probably is not quite as effective as aluminum. Boron should, therefore, be readily oxidized out of the open-hearth bath, which implies that it is not recovered in significant concentration from any scrap charged; also that, if added in the ladle, it tends to oxidize out during teeming unless protected by the presence of a better deoxidizing agent. These conclusions do not apply to liquid cast iron, in which the oxygen content is much lower than in liquid steel. The possibility of conserving certain strategic alloying elements widely used in steelmaking, notably manganese, chromium and molybdenum, by the use of boron, which in small concentration appears to be extraordinarily effective in promoting hardenability, raises a question as to what extent any boron present in the scrap charged into the open hearth is oxidized out during melting and subsequent refining. This question is significant because the optimum concentration of boron in the finished steel, which is fairly critical, would be very difficult to attain if the boron in the charge were largely retained in the metal. Moreover, unless boron is substantially eliminated in the open-hearth process its use on a large scale would eventually make it impossible to produce boron-free steel except by restricting the charge to virgin material. There is at present, unfortunately, virtually no satisfactory direct evidence to provide an answer to this question; but there are indications from practice that boron is oxidized out in the open hearth in the production of medium or low-carbon steel, although it may be retained if the carbon content remains fairly high; that is, if the oxygen is kept fairly low. In the absence of direct data, it is necessary to rely upon the indications of indirect evidence, the best approach now available being a thermodynamic calculation of the deoxidizing power of boron in liquid steel by the general method used so successfully by Chipman1 in his study of the reactions in the open-hearth process. The thermal data for boron, upon which such a calculation must be based, are reasonably satisfactory; the only quantities not directly determined are the entropy of melting of boron, the activity coefficient of boron in liquid steel, and the activity coefficient of B2O3in an open-hearth slag; but these values may be estimated with ample accuracy. The results of this calculation, which is presented later, are given in Table I, together with corresponding data for other deoxidizing elements. This table shows the calculated residual content of oxygen in equilibrium with different residual concentrations of the deoxidizer in the metal;

Jan 1, 1944

By R. W. Gurry

Thermodynamic calculations indicate that boron is a better deoxidizer than silicon but probably is not quite as effective as aluminum. Boron should, therefore, be readily oxidized out of the open-hearth bath, which implies that it is not recovered in significant concentration from any scrap charged; also that, if added in the ladle, it tends to oxidize out during teeming unless protected by the presence of a better deoxidizing agent. These conclusions do not apply to liquid cast iron, in which the oxygen content is much lower than in liquid steel. The possibility of conserving certain strategic alloying elements widely used in steelmaking, notably manganese, chromium and molybdenum, by the use of boron, which in small concentration appears to be extraordinarily effective in promoting hardenability, raises a question as to what extent any boron present in the scrap charged into the open hearth is oxidized out during melting and subsequent refining. This question is significant because the optimum concentration of boron in the finished steel, which is fairly critical, would be very difficult to attain if the boron in the charge were largely retained in the metal. Moreover, unless boron is substantially eliminated in the open-hearth process its use on a large scale would eventually make it impossible to produce boron-free steel except by restricting the charge to virgin material. There is at present, unfortunately, virtually no satisfactory direct evidence to provide an answer to this question; but there are indications from practice that boron is oxidized out in the open hearth in the production of medium or low-carbon steel, although it may be retained if the carbon content remains fairly high; that is, if the oxygen is kept fairly low. In the absence of direct data, it is necessary to rely upon the indications of indirect evidence, the best approach now available being a thermodynamic calculation of the deoxidizing power of boron in liquid steel by the general method used so successfully by Chipman1 in his study of the reactions in the open-hearth process. The thermal data for boron, upon which such a calculation must be based, are reasonably satisfactory; the only quantities not directly determined are the entropy of melting of boron, the activity coefficient of boron in liquid steel, and the activity coefficient of B2O3in an open-hearth slag; but these values may be estimated with ample accuracy. The results of this calculation, which is presented later, are given in Table I, together with corresponding data for other deoxidizing elements. This table shows the calculated residual content of oxygen in equilibrium with different residual concentrations of the deoxidizer in the metal;

Jan 1, 1944

By Molly Gleiser

The standard free energies of formation of some gaseous metal oxides together with those of their condensed oxides have been plotted against temperature. The heats of formation of the gaseozcs oxides are tabulated. An explanation is given of the use of the data to predict the importance of the gaseous metal oxides at high tenzperatures. RECENT mass spectrometric work1 has resulted in the detection of several hitherto unknown gaseous oxides and the measurement of their free energies of formation. Of especial interest is the fact that several of the refractories in common use either as crucibles or furnace tubes, and metals used in Knudsen cells and in furnace windings, have been found to have one or more stable gaseous oxides. In view of the present emphasis on high-temperature techniques, the development of vacuum metallurgy.z heating by electron bombardment and plasma jets, and the resultant shift to ever higher temperatures, it is no longer possible to plan experiments without taking into consideration the significance of the presence of these gases in the system, the reactions they undergo. and their contribution to the vapor pressure. A good example of what went wrong in earlier work, when the existence of these gaseous molecules was not yet known, is presented by the work of Hoch, Nakata, and Johnston. Hoch and coworkers attempted to measure the vapor pressure of solid ZrO2 by letting the vapor in equilibrium with zir-conia effuse from a tantalum Knudsen cell. The free energies of formation of solid zirconia and tantala are such that a short calculation showed that the reaction

Jan 1, 1962