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By K. G. Davis

Dilute alloys of silver and of thallium in tin have been solidijzed unidirectionally under controlled conditions, to study the segregation associated with a cellular interface under conditions where both thermal and solute convection are present. Autoradiography and radioactive tracer counting techniques were combined with electron-probe microanalysis to study both macro- and microsegregation. It was found that, for concentrations giving only small amounts of constitutional supercooling, cell formation had little effect on the macroscopic distribution of solute along the specimen. At higher concentrations the effective distribution coefficient was higher than that expected for a smooth interface. Node spacing was independent of initial solute content at lower concentrations, becoming greater as keff increased. Silver content at the segregation nodes of silver in tin alloys was independent of initial concentration and considerably in excess of the eutectic composition. SINCE the investigation of cell formation at advancing solid-liquid interfaces by Rutter and Chalmers,' a large volume of work has been dedicated to the determination of solidification conditions under which a planar interface will break down into cellular form. Early experiments were explained satisfactorily by the concept of constitutional supercooling,2 but, due to poor measurement of temperature gradients in the liquid, lack of accurate data on liquid diffusion and equilibrium distribution coefficients, and uncertainty about the effects of thermal and solute convection, these experiments cannot be used as proof for the theory. More recent work, however, has shown that under conditions where convection is eliminated or can be ignored good correlation is observed.3,4 Investigations into segregation at cell caps5 and at cell nodes6-'' have been made, but no measurements appear to have been done on the overall, macroscopic segregation down a unidirectionally solidified rod of material which has solidified with a cellular substructure. This has practical importance in casting, where regions of material with cellular substructure are often encountered, and also in zone refining where the thermal conditions necessary for a planar interface are unattainable. Further, as will be shown, the macroscopic segregation can give information on the following question. Granted that a cellular solid-liquid interface develops from a planar one when the conditions for constitutional supercooling are exceeded, how much supercooling is present after the cells have formed? EXPERIMENTAL PROCEDURE AND RESULTS Specimen Preparation. Specimens 25 cm long with a square cross section 0.6 by 0.6 cm were grown in graphite boats by solidification from one end. Alloy compositions are given in Table I. Two specimens of each composition were grown. The tin was 5-9 grade and the silver and thallium both 4-9 grade. Ag110 and Tl204 were used as tracers. Each composition had the same quantity of tracer so that auto radiographs of specimens containing different concentrations of the same element could be easily compared. Thermocouples inserted through the lid of the boat into a dummy specimen showed that, over the first 10 cm of growth, thermal conditions were quite steady, with a rate of interface advance of 5.8 cm per hr and a temperature gradient in the melt ahead of the interface of 3.0°C per cm. The specimens were seeded from tin crystals of a common orientation to eliminate orientation effects. Dilution of the specimen by seed material was minimized by the provision of a narrow neck between specimen and seed crystal. Macrosegregation. After growth, the specimens were sectioned with a spark cutter. The rods of silver alloy were cut into 1-cm lengths and analyzed for Ag110 using a y -ray counter with fixed geometry. The specimens containing thallium were cut into 2-cm lengths and analyzed for T1 204 by taking 13 counts from each end of the cut lengths through an aperture in lead sheet approximately 0.4 cm square. The results are summarized in Figs. 1 and 2. To find the effective distribution coefficient for the silver in tin alloys under smooth interface conditions, the region of substructure at the bottom surface of one of the 10 ppm specimens, see Fig. 3, was removed by spark machining before counting. Autoradiography. For both alloy systems the samples were polished on sections taken alternately parallel and perpendicular to the growth direction, and autoradiographed by placing the polished surfaces in contact with Kodak "Process Ortho" film. Figs. 3 and 4 show the structures revealed. The alloy containing 10 ppm Ag showed substructure only after a few centimeters of growth, and then substructure was limited to a narrow layer at the base. The "speckled" substructure reported previously in this system4 is here clearly seen to be an intermediate stage between planar and cellular interface conditions. The other samples show a remarkable similarity considering

Jan 1, 1969

By F. E. Luborsky, K. T. Aust

RECENT interest has been shown in utilizing solid-state techniques for obtaining large oriented grains in the Alnico Alloys.1-4 Unfortunately, due to the inherent brittleness of these materials it is difficult to introduce sufficient imperfections by deformation to support the nucleation and growth of new, recrystallized grains. As a result, recrystal-lization methods for obtaining large grains, such as the strain-anneal technique, do not appear to be feasible. Steinort et a1.2 used a combination of a thermal gradient and internal strains to obtain large single crystals of Alnico 5 from a poly crystalline casting by annealing at temperatures above 1200°C. It was suggested that the strains were the result of the precipitation of the y phase which exists between -850° and 1200°C. The purpose of the present study was to determine if the grain size of the cast Alnico alloys can be markedly increased by solid state techniques involv-

Jan 1, 1963

Two separate but closely related projects now under construction on the St. Lawrence River- the Seaway and the St. Lawrence Power Project- are providing the impetus for what may become one of the most significant economic expansions in the Northeast. By 1959, or even earlier, electric power will be flowing from the largest single hydroelectric installation east of the Rockies. Simultaneously there will come into existence a great new commercial waterway which will provide cheap transportation from the farm and industrial heartlands of the U. S. and Canada to the markets and resources of the world. When the Seaway is completed, vessels with five to ten times the capacity of those now using the Canadian canal system will be able to move from the Atlantic Ocean to Lake Superior.

Nov 1, 1955

By Leroy W. Weeks, Peter B. Nalle

The rapid growth of the modern electronic computer industry during the past 15 years is, perhaps, the greatest phenomenon that has occurred in American business in this century. This growth is due in part to the new, and in some instances, revolutionary applications of computers instigated and developed by both the manufacturers of such equipment and their customers who search for easier, faster, more accurate methods of conducting their business operations. As in other industries, modern computers are becoming more common in the field of mining. The adaptation of computer analysis to the unique problems of mining companies is undergoing research and development by both electronic and mining companies. However, for those of us in mining who are interested in the possibilities of computer analysis and control, the basic question is Where can a computer system be of use in a mining operation today? Some ideas of such applications follow, as well as a specific example of computer control at the Riverside Cement Co.

Jan 9, 1960

By D. V. Fites

Criteria for deciding when rock should be ripped and what ripping equipment and techniques should be used in given situations are discussed in this article. The relation between ripper performance and seismic wave velocities in various types of rock is also discussed. The ripper is not a new tool. In fact, it dates back as far as the Roman Empire. The Roman's ripper-mounted on wheels and shaped something like a plow — was pulled by oxen and used to loosen the earth for the shovelers and basket carriers building the Appian Way. There are records of rippers being used in this country in railroad construction between 1860 and 1880. However, the ripper as we know it today did not appear until about 1930. Tractor-drawn models were in use in 1931 on the Hoover Dam project. At that time they weighed about 7500 lb and were pulled by tractors with about 75 flywheel hp and up to 30,000 Ib total weight. The chief shortcomings of trailed

Jan 1, 1969

By F. M. F. Cazin

Some twenty years ago the author of a book,* by which, for the first time, molecular action was made to account for nearly all phenomena in hydrodynamics, began his preface as follows: " It is contrary to all experience, that any branch of science should suddenly cut short its own line of reasoning, and drop all connection with its past, and yet as quickly re-establish itself on an entirely new basis. It is, therefore, not without justification that this book should be met with caution and even distrust." When the newly-discovered natural facts and laws presented in this paper were, in 1891, first laid before the officers of the American Institute of Mining Engineers, they might have been preceded by a preface to the same effect; and the expression would have found its justification by the actual experience these facts and laws met with. Since then, as the result of their publication in one of the most prominent

Jan 1, 1895

By Edmund E. Getzin

Of all the developments in the post-war history of Western Europe, none has been more remarkable in its aims and in the progress it has achieved than the movement toward European integration. It is not an exaggeration to say that this movement marks a virtual revolution, an about-face, in the long and complicated history of European states over the past three centuries. Although sporadic efforts to achieve European integration can be traced back for at least a 100 years, it remained for the breakdown of the European economies as a result of World War II and the subsequent Russian threat to give new impetus to the concept of broader economic and political integration. In fact, the economic integration of Europe following the end of the war was considered so essential that, in 1949, the administrator of the European Cooperation Administration, Paul Hoffman, spoke of the economic integration of Western Europe as an objective of American policy embodied in the Marshall Plan.

Jan 6, 1963

By J. J. Lander, L. H. Germer

MOLYBDENUM and tungsten have desirable corrosion and temperature resistant properties, but the metals in bulk are expensive and their fabrication is difficult. Such considerations led to a search for a method of plating them upon base metals. This search was successful and led furthermore to a number of developments which could not have been foreseen. Neither pure tungsten nor pure molybdenum has been electroplated successfully, although the literature of electroplating is liberally sprinkled with the description of unsuccessful attempts. The process of plating these metals by thermal reduction of their halides has achieved only limited usefulness because of technical limitations and because of limited range of product quality. Plating by thermal decomposition of the carbonyls does not suffer from limitations of the same sort and the properties of the plate are readily controllable. This paper describes the plating of molybdenum and tungsten, and of compounds and alloys of these metals, by pyrolysis of their carbonyl vapors. Chromium also has been plated in this manner, but the experiments upon chromium have been less extensive and the results much less satisfactory. Probably the most important of the products which we have obtained are the alloys with carbon, and the carbides of the metals. Either molybdenum or tungsten can be deposited upon a base metal as a coherent and adherent coating. By adjusting the plating condition the carbon content of the coating can be made to have any value from substantially zero to about 35 atomic pct. The hardness is dependent primarily upon the amount of carbon in the plate and can be regulated over a very wide range, some coatings containing considerable carbon being harder than sapphire. In addition to products already known this method of plating has yielded new carbides of molybdenum and tungsten and alloys supersaturated with carbon. These new products are possible because, in the process of plating, carbonyl can be decomposed at temperatures as low as about 150'C, and thus in the presence of other substances reactions occur which could perhaps not be produced in any other way. In addition to carbides and alloys with carbon, sulphides and oxides of molybdenum and tungsten have been produced and studied. There are certain other advantages of the carbonyl method of plating. It is not required that the base have good electrical conductivity as in electrochemical processes, and the base need not have the temperature stability required in plating from a halide. Thus low melting glasses, as well as other ceramics, can be plated almost as readily as metals. In particular, the plating of glass with

Jan 1, 1947

By Wieland D. R., Hurst R. E., A. R. Hendrickson

Analysis of acidizing techniques, in correlation with reservoir data and a backlog of past treatments, has resulted in the development of a valuable engineering guide for planning acidizing treatments. Such treatments fall into three categories: (I) acid injection into the pores of the matrix; (2) acid injection into natural formation fractures at less than parting pressure; and (3) combination acidizing-fracturing treatments in which acid solutions (without propping agents) are injected at treating pressures sufficient to open and extend fractures through which the acid flows. Because the spending tirnze of acid during a specific well treatment does not change appreciably, maximunl penetration is attained when the first increment of injected acid is completely spent. Additional acid injection cannot be expected to further extend the benefits of the treatment. Depth of penetration will depend upon the reaction rate of the acid under treatment conditions, the injection rate of the acid into the matrix or fractures and the area-volume relationship existing in the flow channels. Based on Darcy's flow formula, extremely low injection rates must be used in order to keep bottom-hole injection pressures below formation fracturing pressure. As a result, only limited penetration of unspent acid will occur. Treatment records indicate that, in most acidizing treatments, formation parting pressures are exceeded, greatly extending acid penetration. Under these conditions, stimulation benefits are limited to the fracture area produced during the spending time of the first increment of acid injected into the formation. This area may be calculated from laboratory and well data to estimate depth of penetration. This, in turn, may be correlated with productivity data to assist The art of gas and oil well acidizing has been characterized by many changes in treating materials and techniques since its inception. These developments have been designed to provide greater production increases. prolong production declines and shorten payout time. Such improvements have been based primarily on data derived from laboratory research and field experience. As more of the variables influencing these treatments have been recognized and evaluated, acidizing has become less of an art and more of a science. Recent studies of fracturing treatments,' in light of individual well conditions and the results of thousands of fracturing treatments, made possible the formulation of an engineering guide that is now being used to select optimum treating techniques and to forecast probable results of such treatments. A similar analysis of the factors controlling acidizing treatments has been made and is the basis for this paper, The findings herein can be used as a guide in the selection of acidizing solutions and techniques, tailored to fit specific well conditions and to provide optimum stimulation per dollar cost. Acidizing treatments may be classified into three basic categories—(1) treatments in which the acid is injected uniformly into the pores and flow channels of the matrix, (2) treatments in which the acid enters natural fissures and fractures in the formation at less than fracturing pressures and (3) injection of acid into the formation at a pressure sufficient to open and extend fractures into the rock through which the acid penetrates (without the inclusion of a propping agent). TYPE 1 — MATRIX ACIDIZING This category consists of treatments in which acid solutions are injected into a homogeneous carbonate

By Harvey P. Knudsen, Young C. Kim, Edward Mueller

Abstract-This paper describes the results of a comparative study of the geostatistical ore reserve estimation method over three conventional methods; the polygon method, the inverse of the distance squared (IDS) method, and ELIP which is similar to IDS. Each method was evaluated on its ability to accurately predict individual block grades for one bench of the Pima mine, located near Tucson, Ariz. Results at the Pima mine indicate that the geostatistical method is no better or worse in predicting block grades and total tonnage than the ELIP or IDS methods. In contrast, the polygon method is clearly inferior. All of the methods would have given better results if geology had been included in the block model. At already producing mines ELIP or IDS may be good choices since they involve substantially less cost in computer time. For prospective or new properties the geostatistical model is more attractive due to its ability to construct confidence limits on the estimates.

Jan 1, 1978

C. H. WILSON,* New York, N. Y. (written discussion?).-On page 2680, under the heading Junction Box and Zone Box, the authors say, with reference to the zone-box principle of connections between primary couple, compensator couple, and copper leads, which method in its appli-cation to a single couple is shown in Fig. 34, that if this principle is adopted for a multiple installation, so as to save compensating leads; a selective switch may be (and the inference is that it must be) inserted between the zone box and the different couples, putting the switch at an inconvenient point, or putting up with some complicated interlacing of connections.. Wilson-Maeulen Co. has employed the zone-box method extensively for several years and in none of the many multiple installa-tions has either of those alternatives been resorted to. Instead there has been used a method of wiring with the switch at the indicator and involv-ing no more complications than the junction-box method shown III

Jan 11, 1919

By Thomas Brownfield

The chronicle of the oil industry in Oklahoma in 1939 is one of declining production bolstered by strenuous efforts to find new pools or new producing horizons in the older, highly exploited, relatively shallow areas. Production, which averaged 608,000 bbl. daily in 1937, the post-depression peak, declined to 463,000 bbl. daily in 1938 and continued downward to 421,000 bbl. daily for the year 1939. While the state could produce somewhat more oil if demand warranted it, production in most areas is at as great a rate as could be justified on the basis of maximum efficient operation. Outlet for Oklahoma crude has been seriously affected by the increase in production in the Illinois Basin. Crude movements from the Kansas-Oklahoma area to the northeastern consuming centers averaged 314,000 bbl. daily in 1939 as compared with 397,000 bbl. in 1938. Oklahoma producers bore the brunt of this loss of market. The general production decline was accentuated by the August, shutdown of 15 days, precipitated by the action of a major crude purchaser posting a 20-cent reduction in the price of crude. The Oklahoma Corporation Commission, in collaboration with other members of the Interstate Oil Compact Commission, ordered a complete shutdown of all producing wells in order to prevent the premature abandonment of stripper wells, which might result from a prolonged period of production at prices below operating costs. The reduction in price was forestalled, most major purchasers failing to meet the cut in view of the shutdown, and the company initiating the move rescinded its action. Fear of the shutting in of oil wells, especially those making considerable quantities of water, is generally unfounded in the light of a superficial examination of the records. Oklahoma's unprorated pools, which produced 154,000 bbl. daily in May, declined to 152,000 bbl. in June and 143,000 bbl. in July. Immediately following the shutdown, the same pools produced 150,000 bbl. in September, 145,000 in October, and 145,-000 in November. Thus, while the half month's production loss in August has not been made up, the wells apparently hare produced at a greater rate since the shutdown than immediately preceding it.

Jan 1, 1940

By Thomas Brownfield

The chronicle of the oil industry in Oklahoma in 1939 is one of declining production bolstered by strenuous efforts to find new pools or new producing horizons in the older, highly exploited, relatively shallow areas. Production, which averaged 608,000 bbl. daily in 1937, the post-depression peak, declined to 463,000 bbl. daily in 1938 and continued downward to 421,000 bbl. daily for the year 1939. While the state could produce somewhat more oil if demand warranted it, production in most areas is at as great a rate as could be justified on the basis of maximum efficient operation. Outlet for Oklahoma crude has been seriously affected by the increase in production in the Illinois Basin. Crude movements from the Kansas-Oklahoma area to the northeastern consuming centers averaged 314,000 bbl. daily in 1939 as compared with 397,000 bbl. in 1938. Oklahoma producers bore the brunt of this loss of market. The general production decline was accentuated by the August, shutdown of 15 days, precipitated by the action of a major crude purchaser posting a 20-cent reduction in the price of crude. The Oklahoma Corporation Commission, in collaboration with other members of the Interstate Oil Compact Commission, ordered a complete shutdown of all producing wells in order to prevent the premature abandonment of stripper wells, which might result from a prolonged period of production at prices below operating costs. The reduction in price was forestalled, most major purchasers failing to meet the cut in view of the shutdown, and the company initiating the move rescinded its action. Fear of the shutting in of oil wells, especially those making considerable quantities of water, is generally unfounded in the light of a superficial examination of the records. Oklahoma's unprorated pools, which produced 154,000 bbl. daily in May, declined to 152,000 bbl. in June and 143,000 bbl. in July. Immediately following the shutdown, the same pools produced 150,000 bbl. in September, 145,000 in October, and 145,-000 in November. Thus, while the half month's production loss in August has not been made up, the wells apparently hare produced at a greater rate since the shutdown than immediately preceding it.

Jan 1, 1940

Discussion of the paper of THEODORE P. HOLT, presented at the Salt Lake meeting August, 1914, and printed in Bulletin No. 91, July, 1914, pp. 1699 to 1708. F. S. SCHMIDT, Salt Lake City, Utah.-Any furnace that can make a chloridizing roast to yield an extraction of 92 to 93 per cent. and do this at a cost of less than 24c. per ton in a 10-ton unit opens great possibilities for the treatment of certain classes of ores. This cost does not include the salt and will be reduced to about 16 1/2c. per ton in the 35-ton furnace which are now being designed. On a trial run the roaster treated 9.6 ton: of Ontario stope fillings crushed to pass a ¼ -in. opening. The ore is well adapted to chlorination with the exception of insufficient sulphur and occasional days of high lime, but is not adapted to any other process The following is an analysis of the crude ore: Ag, 9.52; Au, 0.029 oz. Pb, 0.71; Cu, 0.11; SiO, 79.4; Zn, 0.57; S, 1.00; Fe, 7.9; Mn, 0.89 CaO, 1.20 per cent. The composition of the mix was: Per Cent. Dry crude ore : 83.4 Moisture 4.4 Salt 8.3 Coal dust 2.3 Pyrite, 70 per cent. pure 1.6

Jan 11, 1914

By Shun-ichi Satoh

In the previous paper, the writer indicated that the arc welding of cast iron is practicable only when barium carbonate is used to retard the fusion of electrodes. Later, he tested the effects of 48 other elements, to discover the cause of their retarding action. Wrought-iron bars 33 cm. long and 0.53 cm. dia. were used as electrodes. The chemical analysis of the original electrode is given in Table 1. Table 1.—Analysis of Electrode Per Cent. Carbon.................................................. 0.045 Silicon................................................... 0.028 Manganese....................................... Trace Phosphorus.............................................. 0.047 Sulfur................................................... 0.008 Each of the bars was wound with a twine of asbestos (1 mm. dia., weighing 0.5 g.) and then was coated with a mixture of equal quantities of graphite and carborundum and one of the compounds listed in the second column of Table 2. The method used in coating was as follows: The mixtures were reduced to paste by adding to them a solution of water glass (1:3); they were next put in a glass tube of 8 mm. inner diameter, with funnel-shaped mouth (the same tube shown in the previous paper); then the bars were passed through the tube so that the mixtures were coated on them. The glass tube was used only as a means of making the diameters of all coated bars exactly 8 millimeters. The cast iron was deposited on the steel plates by connecting the electrodes first to the positive and then to the negative pole of the generator. The figures representing the time, voltage, amperes and energy required to melt each electrode are given in Table 2. They are arranged in the order of the atomic weights of the elements contained in the coatings. In Figs. 1 to 4, which show respectively the time, current, voltage and energy required in this operation, the abscissas indicate the atomic weights of the elements contained in the coatings, and the ordinates

Jan 1, 1929

By Oliver C. Ralston, Foster Fraas

Electrostatic methods of separation are used only when some peculiar advantage is gained. Such cases are minerals that are not separable by differences in specific gravity or magnetic response and that are desired in particles as large as 10-mesh, a size on which flotation separation is inefficient. This paper covers several separations of this type and others. It includes studies in the electrostatic behavior of kyanite, sillimanite, and zircon, simple silicates that cannot be called either acid or basic but are more nearly neutral. Kyanite and sillimanite are both desired in 10-mesh size and are difficult to bene-ficiate from low-grade ores to give that type of concentrate. A separation of garnet from diopside was studied because this mixture had been removed from a wollas-tonite product by drying and magnetic separation, and no special or extra-preparation for electrostatic separation was necessary. The Separator The separator used in these tests is of the nonhomogeneous field type shown in Fig Ia. It consists of a 11.4-cm-diam rotating metal roll 2 at ground potential over which the dry mixture of minerals is fed. The roll serves as one electrode of the separating field, and the other electrode is that of 3, a smaller 5-cm-diam rotating metal cylinder which is held at a high direct-current potential. In this paper the term "electrode" will be confined to the electrode at 3, roll 2 being designated only as "roll."

Jan 1, 1949

Another excellent Swedish underground crushing plant is that at Crusher Station 51 of LKAB in Kiruna, Sweden. Bottom-dump rail cars pass over a dump scroll to discharge magnetite ore into a 288 cu yd (220 m3) pocket equipped with a Hewitt Robins E-13 vibrating grizzly feeder. The grizzly section is 59 in. (1500 mm) long and has bar spacings 3 in. (76 mm) wide. Any oversize boulders which will not pass the chute opening to the feeder are blasted. The primary breaker is a Morgardshammar overhead eccentric 55 in. by 71 in. (1400 by 1800 mm) jaw crusher powered by a 200 hp (149 kw) motor. An open side setting of 10. 8 to 11. 8 in (275 to 300 mm) accounts for the high capacity of this crushing unit (2760 stph or 2500 mtph). This figure compares favorably with the capacity of many gyratory crushers but is typical of the Swedish jaw crushing installations, which are often followed by three more stages of crushing or by autogenous grinding. Crushed ore from the jaw crusher is combined with the grizzly under- size in the crushed ore pocket and is fed by a second vibrating grizzly feeder to the secondary cone crusher. Both crushers are serviced by 50/5 ton overhead bridge cranes. During maintenance operations air -operated gates shut off the flow of ore from the dump and primary crushed ore pockets.

Jan 1, 1978

PAUL D. FOOTE AND T. R. HARRISON, Washington, D. C. (written discussion *).-There are several methods for measuring the internal resistance of a battery, the line resistance in a circuit containing an e.m.f., or the true value of this e.m.f. The writers, however, were the first to em-ploy a simple principle whereby the total resistance of the circuit is ad-justed to a preassigned value for which the scale of the millivoltmeter is graduated, the only e.m.f. employed being that of the source measured. One of the simplest forms of these instruments is described on page 2842, September Bulletin. In papers now in the press we have described some twenty modifications of this simple design but all operating upon the same fundamentally new principle. The instrument devised by Mr. . Porter is of this general type but, unlike the designs we have recom-mended, is open to serious objections.

Jan 12, 1919

By J. Chipman, N. J. Grant, B. M. Shields

The vacuum tin-fusion method of analysis for hydrogen, developed by Carney, Chipman, and Grant, has been modified to permit the analysis of the evolved gases for hydrogen by means of a thermal conductivity cell. A properly prepared sample can be analyzed in 10 min with a probable error of ±0.12 ppm. A study of various methods for storage of hydrogen samples shows that samples can be safely held in a dry ice-acetone bath as long as six days. Storage in liquid nitrogen is necessary for samples to be held one week or more. HE vacuum tin-fusion method, as developed by I- Carney, Chipman and Grant,' is the only analytical procedure which has shown promise of being fast enough for use in the control of hydrogen during steelmaking. It was felt that further simplification and faster speed of operation could be effected by the use of thermal conductivity measurements for analysis of the gases evolved in the tin-fusion method. The application of conductivity measurements to the tin-fusion method is possible because: 1—the evolved gas is essentially a mixture of hydrogen, nitrogen and carbon monoxide with a hydrogen content usually over 50 pct, 2—the evolved gas is collected at a relatively low pressure, and 3— the thermal conductivities of CO and N2 are practically identical while that of hydrogen is very much greater. The major part of this research program was devoted to the construction and calibration of a vacuum tin-fusion apparatus which analyzes the evolved gases for hydrogen by means of a thermal conductivity cell. The second phase of the problem was associated with the development of a procedure for storage of samples prior to analysis. With the rapid quenching method for hydrogen sampling,' which seems to be the most practical for steel mill use, it is necessary that the samples be stored safely during the interval between sampling and analysis if the hydrogen content of the molten metal is to be maintained in the supersaturated solid samples. The thermal conductivity bridge has been used for a number of years in the analysis of certain gas mixtures. An elementary discussion of the theory and practice of gas analysis by thermal conductivity measurements is given by Minter.3 A more comprehensive discussion of the theory and of the various measuring circuits is presented by Daynes.' A complete knowledge of the theory and properties of the thermal conductivity of gases and gaseous mixtures can be gained by a study of the standard textbooks on the kinetic theory of gases."' The existing data on the thermal conductivity of single gases are reviewed by Hawkins: that for a number of binary gas mixtures by Daynes' and Lindsay." The thermal conductivity method may be applied to the determination of the composition of a binary mixture if: 1—the thermal conductivity of the mixture varies monotonically with composition, and 2— the two gases have measurably different thermal conductivities. The greater the difference between the two gases, the greater the sensitivity of the method.10 he method is applicable to the analysis of multicomponent mixtures when all of the gases in the mixture except one have nearly the same thermal conductivity. Fortunately, the mixture of hydrogen, nitrogen, and carbon monoxide evolved by the tin-fusion analysis' falls in this latter classification. The thermal conductivities of nitrogen and carbon monoxide are practically equal; and the thermal conductivity of hydrogen is approximately seven times that of the other two. Therefore, the thermal conductivity of a gaseous mixture of hydrogen, nitrogen, and carbon monoxide at known temperature and pressure can be related directly to the percentage of hydrogen in the mixture by suitable calibration. Usually the thermal conductivity of a mixture of gases is measured at atmospheric pressure where the thermal conductivity is independent of pressure over a wide pressure range. At very low pressures (below 1 mm Hg), the thermal conductivity of gases varies with the pressure. This phenomenon has been utilized in the Pirani vacuum gage for the measurement of pressures in the range of 10" to 10-0 mm of mercury.= Very little has been published concerning the variation of thermal conductivity with pressure at intermediate pressures between 1 mm Hg and 1 atm. However, preliminary measurements indicated that the thermal conductivities did vary with pressure over the range of pressures (up to 10 mm Hg) at which gases are delivered from the vacuum pump. Therefore, the calibration of the thermal conductivity cell had to be planned to include the effects of both gas composition and pressure. Such a calibration chart is shown in Fig. 4. Most industrial applications of the thermal conductivity method of gas analysis have used a compensated Wheatstone bridge circuit containing two

Jan 1, 1954

By H. D. Colson, Robert A. Rapp

When a binary alloy is oxidized to form simultaneously an internal oxidation zone and an external scale which grows at a constant rate, the oxidation should reach a condition of steady shale, in which the internal oxidation zone is maintained at a time-independent thickness. Assuming an ideal model for the steady-state oxidation, the diffusion equation is solved for the steudy-state concentration profiles for oxygen and alloying- element in the metal. A theoretical prediction of' the steady-state thickness of the internal oxidation zone is made in terms of the experimental parameters. FOR the oxidation of binary alloys, Rhines, Johnson, and Anderson,1 as well as Mask: have derived equations describing the kinetics for the simultaneous formation of an internal oxidation zone and an external scale which was assumed to mow according to a parabolic rate law. Experimental determinations of internal oxidation zone thicknesses beneath a Cu2O scale for Cu-Be and Cu-A1 alloys3,4 have shown some deviation from Maak's theoretical expressions, because the ideal model assumed for the calculation is not met experimentally. Some pure metals, such as columbium and tantalum oxidize at elevated temperatures and high oxygen pressures to form nonprotec-tive external scales which thicken at a constant rate. If such a base metal is alloyed with a solute element which may form a more stable oxide than the solvent oxide, then internal oxidation of solute may occur beneath the growing external scale. A review of the internal oxidation of alloys has been published recently.5 The purpose of this paper is to analyze theoretically for a binary alloy the kinetics for the simultaneous formation of an internal oxidation zone and an external scale which grows at a constant rate. Consider an alloy A-B in which A is the more-noble solvent and B is the less-noble solute. The solute oxide is assumed to precipitate in internal oxidation as stoichiometric particles of BO, which are assumed to have a negligible solubility product in the A matrix. It is further assumed that the diffusion of oxygen through the zone of internal oxidation is not impeded by previously precipitated BO, particles. The specimen is assumed to be sufficiently thick so that the solute content in the center of the specimen does not change. For consistency: the following notation of Maak2 has been used:

Jan 1, 1967