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By Charles H. White

Methods in colorimetry are based on the assumption that the intensity of the' color of a definite volume .of solution is directly proportional to the quantity of the color-producing substance present. In the preparation and examination of colored solutions there are three ways in which the depth of color may be varied. These variables are : (1) the quantity of' the coloring matter; (2) the quantity of the solvent, or the dilution ; and (3) the thickness or depth of that portion of the solution examined. With these three variables as a basis, three general methods in colorimetry have been devised, all of which have been used in the determination of carbon in steel. In the first method, the quantity of the solution is kept the same for both the unknown steel and the standard, and the sections compared are of equal thickness, while the quantity of the standard is varied until the color obtained is of the same intensity as that produced by a definite quantity of the unknown steel. In laboratories where this method is used there is prepared and kept for permanent use a series of solutions with varying amounts of the standard, representing the percentages of carbon from the lowest to the highest demanded in that laboratory. These standard solutions are kept in bottles or test-tubes of equal diameter, and are arranged in series from the faintest to the most intense color, so that it is a simple matter to find the place of the unknown steel in the series, when the solution is of a definite volume and is contained in a tube of the same diameter as the standard tubes. In the second method, equal quantities of the standard and of the unknown steel are dissolved, the standard is diluted to a definite volume, and the solution of the unknown steel is di-

Jan 1, 1907

By Evan Just

Government aid, regulation, and participation in the mineral industry are not new; they date back to the time when man first adopted communal living. Even in primitive tribal life, the obtaining of arrowhead or ceramic materials, washing of gold, or mining of copper were specialized activities, under tribal sponsorship. Later, when kingdoms, dynasties, and hierarchies developed, titles to mining properties were held by the sovereign or the state, work usually being done by slaves. Title acquisition through denouncement developed in Europe in the late Middle Ages and spread to the Western Hemisphere with the Spanish and Portuguese empires. Denouncements still recognized the rights of the sovereign in the requirement to pay royalties, which practice continues in many places today. Thus, anyone who views government participation in mineral activity as "encroachment" has no historical perspective. Only in a few countries and for a few generations have private interests enjoyed the right to exploit mineral deposits without the specific consent of the sovereign or without payment-of-royalty. Governments and the mineral industry have been linked together by other factors. Governments have had special interest in metals and minerals as stores of value and for armaments. Spanish conquests in the New World were energized by the lure of gold and silver. Pursuit of gold led to the American seizure of California in the days of the Forty-niners. The strategic importance of minerals in our own times has called for special steps to stimulate production in national emergencies and to prevent the enemy from acquiring mineral supplies. Our export controls to deny certain minerals to unfriendly countries, purchases for Government stockpile, and subsidies for domestic production are examples. Production regulation by state governments of oil and gas has become a well established routine. In brief, the mineral industry has never lacked aid, regulation, and participation by governments. The entrepreneur who wishes to explore for or develop minerals must deal with governments in most areas before he can begin, because mineral rights are reserved by them. He can proceed through discovery and de-

Jan 1, 1959

By J. Iannicelli

Availability of large-scale high field/high gradient magnetic separators during the past five years allows applications of magnetic separation to feebly paramagnetic materials which have been considered nonmagnetic in the past. Technology is now available for magnetically attracting not only feebly magnetic compounds of iron such as hematite and pyrite, but also hundreds of compounds of nonferromagnetic elements such as copper, tin, uranium, vanadium. Besides enabling novel separation of industrial minerals, metallic ores, and coal, the new technology also can be used in effluent treatment, catalyst cleanup, and purification of chemicals.

Jan 1, 1979

By W. V. Bluck, W. L. McMorris

Higher coal quality is being recognized in potentially lowering the cost of power as measured at the bus bar. Assessment of potential coal supplies for most power plants is now going beyond buying at the lowest delivered fuel cost. It is now taking into consideration other factors, such as handling, storage, pulverization cost, boiler fouling, post combustion cleanup, and waste disposal costs. New measurements of quality are being considered now by those producing and those consuming the fuel by assessing numerous variables in the total fuel cycle to achieve the lowest possible power costs.

Jan 1, 1986

By Evan Just

Government aid, regulation, and participation in the mineral industry are not new; they date back to the time when man first adopted communal living. Even in primitive tribal life, the obtaining of arrowhead or ceramic materials, washing of gold, or mining of copper were specialized activities, under tribal sponsorship. Later, when kingdoms, dynasties, and hierarchies developed, titles to mining properties were held by the sovereign or the state, work usually being done by slaves. Title acquisition through denouncement developed in Europe in the late Middle Ages and spread to the Western Hemisphere with the Spanish and Portuguese empires. Denouncements still recognized the rights of the sovereign in the requirement to pay royalties, which practice continues in many places today. Thus, anyone who views government participation in mineral activity as "encroachment" has no historical perspective. Only in a few countries and for a few generations have private interests enjoyed the right to exploit mineral deposits without the specific consent of the sovereign or without payment of royalty. Governments and the mineral industry have been linked together by other factors. Governments have had special interest in metals and minerals as stores of value and for armaments. Spanish conquests in the New World were energized by the lure of gold and silver. Pursuit of gold led to the American seizure of California in the days of the Forty-niners. The strategic importance of minerals in our own times has called for special steps to stimulate production in national emergencies and to prevent the enemy from acquiring mineral supplies. Our export controls to deny certain minerals to unfriendly countries, purchases for Government stockpile, and subsidies for domestic production are examples. Production regulation by state governments of oil and gas has become a well established routine. In brief, the mineral industry has never lacked aid, regulation, and participation by governments. The entrepreneur who wishes to explore for or develop minerals must deal with governments in most areas before he can begin, because mineral rights are reserved by them. He can proceed through discovery and de-

Jan 1, 1964

By G. R. Kotler, W. A. Tiller, W. C. Johnston

Experiments carried out on 100 g samples of molten tin and Sn-Pb alloys showed that the magnitude of the field strength, H, does not effect the supercooling, aTn, at which the initial nucleus of solid forms. However, the nuwlber of nuclei forming per cc, n, is found to increase greatly with H for fixed ATN and to increase with ATN for fixed H. The value of n increases greatly with the presence of solute and is found to he indefiendent of the cooling rate of the simples. Further, the most effective time for stirring to enhance n is immediately following the initiation of recalescence. The effect of inducing nucleation with the aid of a mechanical impact both in the presence and absence of stirring has also been studied. All proposed mechanisms for the enhancement of n by physical means seem to be inadequate in accounting for these results. IN any real nucleation experiment there are two effects influencing the results that would not be predieted from classical homogeneous nucleation theory. These may be separated into chemical and mechanical effects. The chemical effects are twofold. 1) Nucleation catalysts are present which enhance the nucleation frequency of new grains over that predicted by classical homogeneous nucleation theory.' 2) Solute will restrain the growth of nuclei so that many others may form.2,3 The mechanical effects are also two-fold. 1) Vibration (sonic or ultrasonic) of the freezing liquid enhances the nucleation frequency of new grains over that given by the chemical effects alone.4-6 2) Macroscopic fluid-flow effects produce the same effect as l).'7' It is also possible to influence the nucleation experiment by certain physical effects such as the application of electric and magnetic fields.9 From classical homogeneous nucleation theory one would predict the following relationship between the nucleation rate, N1 (number of nuclei formed per unit volume per unit time), and bath supercooling, AT, for an isothermal experiment.

Jan 1, 1963

By John A. Wolfe, James A. Niederjohn

Applications of mathematical statistics to the field of exploration are still relatively new. There are two primary reasons why little has been published in this field. First, if one discovers an effective technique for exploration, he does not like to disclose it. Second, the geologist needs to work closely with a mathematical statistician, and the communications barrier between the disciplines is formidable. The authors, one a geologist and the other a statistician, were interested in the economic benefit which appeared to be possible in the inter-disciplinary area they call "geostatistics."

Jan 11, 1962

By Adrian E. Ross

Diamond drilling through caving formations at depths greater than ZOO0 ft has long presented serious difficulty, generally solved either by casing or cementing. Casing is permitted only when the resulting smaller hole is acceptable, and cementing is frequently a problem at depth. A new method that injects cement under pressure at the desired location is an aid in diamond drilling deep holes. DRILLING through caving formations in diamond drill holes at depths greater than 2000 ft has long been a serious problem. These caving formations are normally passed only by casing the hole or by cementing the hole. Casing the hole is possible only when a resulting smaller hole is acceptable. In as much as only a limited number of reductions are economically practical, cementing is frequently considered the only method suitable for solving these problems. Cementing either by pumping a slurry into the hole or by dropping cylinders containing cement has proved satisfactory on holes under 2000 ft. In holes substantially deeper than 2000 ft these methods are not satisfactory, since during the pump- ing process cement separates out, whereas cylinders usually break before the bottom of the hole is reached. A new procedure, the injector method, apparently solves these problems.* With this method, cement is lowered in the hole in a cylinder, the cement being

Jan 1, 1953

By Adrian E. Ross

Diamond drilling through caving formations at depths greater than ZOO0 ft has long presented serious difficulty, generally solved either by casing or cementing. Casing is permitted only when the resulting smaller hole is acceptable, and cementing is frequently a problem at depth. A new method that injects cement under pressure at the desired location is an aid in diamond drilling deep holes. DRILLING through caving formations in diamond drill holes at depths greater than 2000 ft has long been a serious problem. These caving formations are normally passed only by casing the hole or by cementing the hole. Casing the hole is possible only when a resulting smaller hole is acceptable. In as much as only a limited number of reductions are economically practical, cementing is frequently considered the only method suitable for solving these problems. Cementing either by pumping a slurry into the hole or by dropping cylinders containing cement has proved satisfactory on holes under 2000 ft. In holes substantially deeper than 2000 ft these methods are not satisfactory, since during the pump- ing process cement separates out, whereas cylinders usually break before the bottom of the hole is reached. A new procedure, the injector method, apparently solves these problems.* With this method, cement is lowered in the hole in a cylinder, the cement being

Jan 1, 1953

By Walter Miller

Any annual review of engineering progress in petroleum refining must of necessity include many features mentioned in earlier reviews. Advances do not spring mushroom fashion to wide acceptance overnight, but rather resemble rolling snowballs, gathering size and velocity as they progress. The new ideas of one year develop through the course of scattered adoption and testing during following years, to be ultimately discarded or to become an integral part of refinery engineering and operation. Polymerization and Cracking As an illustration, the publicity given to the polymerization and cracking of petroleum gases during the year has given many the impression that this is a new art. But patent and technical literature have disclosed active work on the problem dating back a decade or more and a unit capable of making 100 bbl. a day of polymer gasoline was constructed as early as 1930. Important strides have been made during 1935 looking to the more general commercialization of available processes, and some four important groups are furthering this work. In addition to the production of liquid products for inclusion as a constituent of commercial motor fuel, polymerization has also been a factor leading to the installation of a plant at the Houston refinery of The Shell Petroleum Corporation for manufacturing isooctane for aviation use, by making available dibutylene for catalytic hydrogenation Polymerization is not confined to unsaturated hydrocarbon gases as a source of raw material, and has been extended to include a preliminary decomposition of normal saturated gases under suitable heat and pressure conditions into the unsaturated types, which can then be used as raw material for the polymerization process. Thus there is opened up the possibility of eventually using large quantities of natural gas in the manufacture of high-grade motor fuels, although the early commercial growth will be largely on cracking still gases for economic reasons. Such utilization will result in a somewhat lowered drain on crude-oil reserves and a partial elimination of the

Jan 1, 1936

By Walter Miller

Any annual review of engineering progress in petroleum refining must of necessity include many features mentioned in earlier reviews. Advances do not spring mushroom fashion to wide acceptance overnight, but rather resemble rolling snowballs, gathering size and velocity as they progress. The new ideas of one year develop through the course of scattered adoption and testing during following years, to be ultimately discarded or to become an integral part of refinery engineering and operation. Polymerization and Cracking As an illustration, the publicity given to the polymerization and cracking of petroleum gases during the year has given many the impression that this is a new art. But patent and technical literature have disclosed active work on the problem dating back a decade or more and a unit capable of making 100 bbl. a day of polymer gasoline was constructed as early as 1930. Important strides have been made during 1935 looking to the more general commercialization of available processes, and some four important groups are furthering this work. In addition to the production of liquid products for inclusion as a constituent of commercial motor fuel, polymerization has also been a factor leading to the installation of a plant at the Houston refinery of The Shell Petroleum Corporation for manufacturing isooctane for aviation use, by making available dibutylene for catalytic hydrogenation Polymerization is not confined to unsaturated hydrocarbon gases as a source of raw material, and has been extended to include a preliminary decomposition of normal saturated gases under suitable heat and pressure conditions into the unsaturated types, which can then be used as raw material for the polymerization process. Thus there is opened up the possibility of eventually using large quantities of natural gas in the manufacture of high-grade motor fuels, although the early commercial growth will be largely on cracking still gases for economic reasons. Such utilization will result in a somewhat lowered drain on crude-oil reserves and a partial elimination of the

Jan 1, 1936

By A. D. Mutch

IT has long been known that there are wide variations in the thermo-electric potential of pyrite. In the last few years a study of this variation and other properties of pyrite was carried out at the University of Toronto by F. G. Smith on specimens of pyrite from many loyalities. As a result of these studies the pyrite geothermometer was developed by Professor Smith. The calibration of the pyrite geothermometer is based on the assumption that "crystals of any one electronically conducting mineral species deposited at a high temperature have a more positive thermoelectric potential than crystals deposited at a low temperature, and the thermo-electric potential varies continuously between any given limits of the temperature of deposition." The cause of the variation was postulated to be crystal discontinuities, such as lineage boundaries. As yet this postulated relationship has not been established as fact. On theoretical grounds it is indicated that the thermo-electric potential of pyrite or any other partial conductor is dependent upon a number of factors as well as the temperature of formation. For this and other reasons there is ground for doubt as to the validity of the relationship postulated above. To date a large number of readings have been made with the pyrite geothermometer which have been recorded in terms of the calibration of the instrument in degrees centigrade. So far most of the pyrite tested by this technique has been in association with gold ore. The values for the temperature of formation obtained in these tests appear to be reasonable and, in relation to geological problems, to vary in the right sense. Determinations on some specimens not in association with gold ore have given readings that appear to be much too high, taking into account the probable maximum temperature of the host rock. To sum up, although many determinations made with the pyrite geothermometer appear to give reasonable values for the temperature of formation of the pyrite, there are at the same time other readings which seem anomalous. On the basis of an examination of available results of work with the pyrite geothermometer, two problems must be considered: 1—the validity of the calibration of the pyrite geothermometer; and 2— the nature of the distribution of the thermo-electric potentials of pyrite in relation to the specific problems that have been examined. In this paper the academic problem relating to the validity of the calibration of the pyrite geothermometer will not be discussed. Instead, the variations of thermo-electric potential of pyrite in association with gold veins will be discussed with regard to specific examinations. The first of these two examinations deals with the distribution of thermo-electric potentials of pyrite in association with a gold vein and was carried out in the McIntyre Porcupine Mine, Schumacher, Ont., in the summer of 1949 as part of a study with this technique. The second problem deals with variations of thermo-electric potential of pyrite in gold ore specimens from all over the world. The specimens used in this study were part of the private collection of Frank Ebbutt, geologist for Howe Sound Exploration Co. Results of Detailed and Reconnaissance Studies In discussion of the results of determinations made in these two studies the values of thermo-electric potential in millivolts will be used. It will be noted that in some of the diagrams the determinations are recorded in terms of pyrite geothermometer temperatures. Fig. 1 is a calibration chart relating pyrite geothermometer temperatures and thermoelectric potentials. A full discussion of the technique is given in the original paper by F. G. Smith.' Briefly, the determinations are made by placing two stainless steel probes, one hot and the other cold, against the surface of the pyrite crystal being tested. The thermoelectric potential that is developed is read with a null-point potentiometer that is calibrated in what

Jan 1, 1953

By A. D. Mutch

IT has long been known that there are wide variations in the thermo-electric potential of pyrite. In the last few years a study of this variation and other properties of pyrite was carried out at the University of Toronto by F. G. Smith on specimens of pyrite from many loyalities. As a result of these studies the pyrite geothermometer was developed by Professor Smith. The calibration of the pyrite geothermometer is based on the assumption that "crystals of any one electronically conducting mineral species deposited at a high temperature have a more positive thermoelectric potential than crystals deposited at a low temperature, and the thermo-electric potential varies continuously between any given limits of the temperature of deposition." The cause of the variation was postulated to be crystal discontinuities, such as lineage boundaries. As yet this postulated relationship has not been established as fact. On theoretical grounds it is indicated that the thermo-electric potential of pyrite or any other partial conductor is dependent upon a number of factors as well as the temperature of formation. For this and other reasons there is ground for doubt as to the validity of the relationship postulated above. To date a large number of readings have been made with the pyrite geothermometer which have been recorded in terms of the calibration of the instrument in degrees centigrade. So far most of the pyrite tested by this technique has been in association with gold ore. The values for the temperature of formation obtained in these tests appear to be reasonable and, in relation to geological problems, to vary in the right sense. Determinations on some specimens not in association with gold ore have given readings that appear to be much too high, taking into account the probable maximum temperature of the host rock. To sum up, although many determinations made with the pyrite geothermometer appear to give reasonable values for the temperature of formation of the pyrite, there are at the same time other readings which seem anomalous. On the basis of an examination of available results of work with the pyrite geothermometer, two problems must be considered: 1—the validity of the calibration of the pyrite geothermometer; and 2— the nature of the distribution of the thermo-electric potentials of pyrite in relation to the specific problems that have been examined. In this paper the academic problem relating to the validity of the calibration of the pyrite geothermometer will not be discussed. Instead, the variations of thermo-electric potential of pyrite in association with gold veins will be discussed with regard to specific examinations. The first of these two examinations deals with the distribution of thermo-electric potentials of pyrite in association with a gold vein and was carried out in the McIntyre Porcupine Mine, Schumacher, Ont., in the summer of 1949 as part of a study with this technique. The second problem deals with variations of thermo-electric potential of pyrite in gold ore specimens from all over the world. The specimens used in this study were part of the private collection of Frank Ebbutt, geologist for Howe Sound Exploration Co. Results of Detailed and Reconnaissance Studies In discussion of the results of determinations made in these two studies the values of thermo-electric potential in millivolts will be used. It will be noted that in some of the diagrams the determinations are recorded in terms of pyrite geothermometer temperatures. Fig. 1 is a calibration chart relating pyrite geothermometer temperatures and thermoelectric potentials. A full discussion of the technique is given in the original paper by F. G. Smith.' Briefly, the determinations are made by placing two stainless steel probes, one hot and the other cold, against the surface of the pyrite crystal being tested. The thermoelectric potential that is developed is read with a null-point potentiometer that is calibrated in what

Jan 1, 1953

By G. C. Weaver, G. T. Harley

BEDS or lenses of potash and magnesium salts are found in a thick salt section (Salado) overlain by Rustler Red Beds in several members of which water is present and from one of which the refinery process water used by International is obtained. Most of the holes drilled are less than 1000 ft. deep, but some wildcat holes have exceeded 3000 ft. Cable or rotary tools are used to drill down to the salt. When samples of water are desired the cable rig is used, but when this is not necessary, and where caving material is present, the rotary rig has an advantage. The rotary rig has a further advantage in that only one machine is required to drill and core the entire hole, whereas the cable rig must be moved off to make way for the core drill. Casing is placed in the upper section of the hole as required to shut off water, and a 5 3/16-in. string is set in the top of the salt before coring starts. With the rotary rig drilling is often carried to the salt with no casing, as drilling mud seals off caving ground and water-bearing strata, and a string of 4-in, line pipe or 4-in. flush-joint casing is landed on top of salt. Several types of gasoline-powered core rigs have been used in the field and all recover a 2 1/2-in. core. More recently the Sullivan Model 37 rotary rig has been tried, and a Sullivan Model N has been adapted to use a rotary bit in the upper section. Core is recovered in 20 ft. sections with a double-tube core barrel, and the bit used is a bottom-discharge type set with diamonds. The drilling fluid must be a saturated brine to prevent solution and etching of the minerals present. Blowouts are apt to occur from nitrogen gas trapped under the several polyhalite beds, and some have been strong enough to blow the tools out of the hole. Core recovery is practically 100per cent. All holes are plugged after drilling, with cement through the salt section and opposite each water horizon, and mud through the remainder of the hole. Cores are carefully logged and preserved, and in sections containing potash and magnesium minerals they are quartered and analyzed. The correlation of ore beds between drill holes is briefly described.

Jan 1, 1946

By Joseph Pogue

THE past year in the petroleum industry was one of overproduction, rising inventories, low prices, and meagre to vanishing profits. This outcome was the result of a long period of intensive and uncompensated effort on the part of both financial and industrial interests, to stimulate supply on the theory that the primary problem facing the petroleum industry was the development of an adequate reserve of raw material to protect a large and ever-growing investment. The stimulus was applied in various forms and through diverse channels: capital had, long flowed into the industry in excessive amounts under the attraction of large expected profits; the price level for crude petroleum had persistently been influenced -by speculative considerations, with the result that prices declined slowly in periods of flush production and were quick to advance in anticipation of statistical improvement, thus maintaining a superfluous degree of stimulus on wildcatting and on drilling; speculation in inventories had led to the unsound, or at least unusual, business practice of accumulating huge stocks of oil; and, above all, the industry had directed the potent force of technology to the expansion of supply and achieved radical results in accelerating oil discovery, speeding up the rate of oil extraction, and enlarging the recovery of gasoline and lubricating oils from the raw material. In short, the economic conditions of 1927 were exactly those to which the objectively driven enterprise of the petroleum industry had long been directed; and the undesirable financial consequences arising. therefrom reflected no lack of success in what had been set out to be achieved, but rather the failure to have established concurrently the necessary means of economic control to prevent the immediate conversion of reserves into current supply, and likewise the oversight in neglecting to apply the technological force to the enlargement and diversification of the market for petroleum products. Perhaps, when viewed in its longer perspective, 1927 will stand out as the turning point in the economic policy of the petroleum industry, when the technique of rationalizing production made its, initial claim for recognition.

Jan 1, 1928

By W. H. Hoffman

The writer does not claim a right to discnss this subject as a furnace-man or user of iron-ore in this new form. His efforts have been confined to mining, preparing, and separating the magnetic ore from the gangue. Two years' experience in experimenting and another two years in producing concentrates on a commercial scale, have led me to believe that the new trade of making concentrates must be well learned in all of its details. If there have been any partial failures in this most useful branch of the iron business, the failures have been caused chiefly by inexperience or lack of patience. Although I have, within the past five years, constructed machinery

Jan 1, 1892

Discussion of the paper of L. W. BAHNEY, presented at, the New York meeting, February, 1915, and printed in Bulletin No. 9S, February, 1915, pp. 339. to 344. E. J. HALL,* New York, N. Y. (communication to the Secretary+).- The Chiddy method for determining gold and silver in cyanide solutions has been subjected to so many proposed modifications, of which L. W. Bahney's is one, it is natural to suppose the method is defective. There is no denying that this method is capable of giving inaccurate results, but so is any other method of quantitative determination. However, proof has not come to my notice that the troubles are inherent and not in the detail application, and I am inclined to think from our experience that in many cases it is the latter. Errors in this method may be occasioned by: (1) The retention of zinc in the sponge, which tends to desilverize the molten lead in cupellation, similar to the action in the Parkes process, removing gold and silver in a crust of zinc oxide. Failure to remove zinc may result from lack of concentration of hydrochloric acid, clue to neutralization by salts present, volume of liquid too great for the specified amount of acid, or the use of weak acid. (HCl rapidly loses its strength unless kept in perfectly tight containers. The HCl gas escapes even from the ordinary glass-stoppered acid bottles after the plaster seal has been broken.) Undissolved zinc, is likely to be held in the upper part of the lead sponge, which floats above the liquid, and unless the solution is boiled it will escape action. Mr. Bahney's modification makes this

Jan 5, 1915

By W. A. Tiller

The unidirectional freezing of a semiinfinite liquid from one end has been treated by calculating the solute and temperature distributions in the liquid and solid phases with time, when the solid-liquid interface advances at a rate proportional to (time)lt2. The nucleation probability for new grain formation is calculated as a function of the constitutional and thermal properties of the alloy, the pouring conditions and the catalytic efficiency of the nucleating agents. The transition from columnar crystal formation to equiaxed crystal formation is assumed to occur at a critical nucleation frequency for a particular alloy and the quantitative dependence of the ratio (columnar zone length/equiaxed zone length) upon the freezing conditions has been predicted. The effects of (i) fluid flow in the liquid, (ii) heat transfer through a mold wall, and (iii) a finite ingot length, have been explicitly tveated as departures from ideality. These departures from ideality are found to have very important consequences on the ingot stmcture. In Part I&apos; of this series, a qualitative description of the general ingot structure was developed. The factors that determine i) the ratio of the equiaxed zone length to columnar zone length and ii) the grain sizes in these zones, were discussed. In the present paper, topic (i) will be treated quantitatively, and it is intended that topic (ii) will be treated quantitatively in Part 111. The complete treatment has been split in this manner for ease of development and coherency of presentation. The treatments are quite mathematical in nature and, although some of the conclusions to Part 11 depend upon the treatment presented in Part 111, it was felt that the intended audience would find the material more readable and more useful in its present form. To this same end, it seems worthwhile to reiterate some of the qualitative aspects of grain nucleation during ingot solidification before embarking on the mathematical description. QUALITATIVE ANALYSIS In the conventional method of casting, a liquid alloy with a certain degree of superheat is poured into a mold. The outer rim of liquid metal cools rapidly to the liquidus temperature of the alloy and begins to undercool. As the degree of undercooling increases, nuclei of solid begin to form in this chill layer, this nucleation being catalyzed by certain heterogeneous particles in the liquid. The grains in the chill layer which are generally of random orientation, begin to grow inwards because of heat conduction through the mold. The grains usually develop a columnar shape since the frequency of nucleation of new grains in the liquid ahead of the advancing interface is generally insufficient to seriously impede the growth of the original grains. Due to the slow diffusion rate of solute in the liquid, a solute distribution is formed in the liquid adjacent to the interface which is either an excess or a depletion if the partition coefficient, ko, of the solute is < 1 or > 1, respectively. Thus, the liquidus temperature of the liquid adjacent to the interface is a function of position. The actual temperature in the liquid is also a function of position and the temperature gradient at the interface decreases as the interface moves away from the mold wall. Since the rate of advance of the interface decreases with time, the equilibrium temperature distributions and the actual temperature distributions as a function of interface position, X, can be illustrated as in Fig. 1. Thus, a region of liquid may exist in which the actual temperature is below the liquidus temperature. This liquid is contitutionally supercooled and therefore unstable with respect to the nucleation of new grains. Now, since the supercooling in Fig. 1 increases as the interface moves further away from the mold wall, the nucleation rate of new grains will increase. When the nuclea-

Jan 1, 1962

By James M. Stapleton

IT has long been recognized by blast- furnace men that correct top distribution of materials is very important in efficient and economical furnace operation. Thousands of experiments on top design, filling, sizing, and other operations have been carried out to improving furnace performance by securing uniform distribution. Many of these experiments have worked out satisfactorily and have been passed along to the industry. Many of them have been discarded and forgotten. It has been the custom to judge the results of such experimentation by the results shown in improved or lowered furnace efficiency. While the effect on furnace practice will have to continue to be the final criterion of experimental changes, it has always been a desire of blast-furnace men to ascertain the reason for failure or success. Efficiency in the blast furnace approaching the maximum can be measured in several ways: (I) by actual operating results as revealed in the coke rate and tonnage figures, and (2), in the degree to which the top gas approaches the limiting ratio of CO/C02 for the reduction of iron oxide by CO gas. This ratio is shown in the equilibrium curve in Fig. I for the system Fe-O-C and CO2-CO-C. The closer the top gases approach this limiting ratio (set at 1.08 by Martin1 because of the effect of limestone calcination) the more efficiently we may expect a furnace to operate. The fact that low CO/C02 ratios parallel eficient operating performance caused us to investigate the cause of good or poor distribution and the effect of filling and other changes on furnace operation. Heretofore it has been possible to take a sample of furnace gas (usually from the dust catcher) and from it determine how closely the reducing gases were to the ideal or limiting value as set by the equilibrium diagram. However, to find just where in the top area the distribution was distorted and the top-gas CO/CO2 ratios were distant from equilibrium values has been a difficult and expensive investigational procedure. In an effort to overcome this difficulty, apparatus was designed to take gas samples and temperatures across the top radius of the furnace. It was hoped that with the aid of this apparatus traverse sampling of the ascending gases could be simplified, and the cost of sampling substantially lowered. Routine experimenting could then be maintained and results checked with furnace operation. It must be emphasized that a traverse sampling is necessary for a true picture, as single samples at any one point are unreliable. This statement can be verified by an examination of Tables 3 to 6, showing results obtained at our furnaces in a large number of tests. APPARATUS The design of the equipment for taking the samples was governed by the need for providing a simple, routine test that could be performed fairly quickly without adversely affecting normal furnace operation.

Jan 1, 1943

By W. R. Hibbard

THE classical work on the electrical conductivity of alloys was carried out by Matthiessen and his coworkers1 in the early 1860&apos;s. He attempted to correlate the electrical conductivity of alloys with their constitution diagrams, but the information regarding the latter was too meager for success. Guertler2 reworked Matthiessen&apos;s and other conductivity data in 1906 on the basis of volume composition (an application of Le Chatelier&apos;s principle with implications as to temperature and pressure effects), and obtained the following relationships between specific conductivity and phase diagrams (plotted as volume compositions) : 1—For two-phase regions, electrical conductivity can be considered as a linear function of volume composition, following the law of mixtures. 2—For solid solutions, except intermetallic compounds, the electrical conductivity is lowered by solute additions first very extensively and later more gradually, such that a minimum occurs in systems with complete solid solubility. This minimum forms from a catenary type of curve. Intermetallic compound formation with variable compound composition results in a maximum conductivity at the stoi-chiometric composition. Landauer" has recently considered the resistivity of binary metallic two-phase mixtures on the basis of randomly distributed spherical-shaped regions of two phases having different conductivities. His derivation predicts deviations from the law of mixtures which fit measurements on alloys of 6 systems out of 13 considered. Volency (Ionic Charge) Perhaps the first comprehensive discussion of the electrical resistivity of dilute solid-solution alloys was presented by Norbury&apos; in 1921. He collected sufficient data to show that the change in resistance caused by 1 atomic pct binary solute additions is periodic* in character. The difference between the period and/or the group of the solvent and solute elements could be correlated with the increase in resistance. Linde5-7 determined the electrical resistivity (p) of solid solutions containing up to about 4 atomic pct of various solutes in copper, silver, and gold at several temperatures. He reported that the extrapolated"" increase in resistance per atomic percent addition is a function of the square of the difference in group number of the solute and solvent as follows: ?p= a + K(N-Ng)2 where a and K are empirical constants and N and Ng are group numbers of the constituents. This empirical relation was subsequently rationalized theoretically by Mott,8 who showed that the scattering of conduction electrons is proportional to the square of the scattering charge at lattice sites. Thus, the change in resistance of dilute alloys is propor-t,ional to the square of the difference between the ionic charge (or valence) of the solvent and solute when other factors are neglected. Mott&apos;s difficulty in evaluating the volume of the lattice near each atom site where the valency electrons tend to segre-gate: limited his calculations to proportionality relations. Recently, Robinson and Dorn" reconfirmed this relationship for dilute aluminum solid-solution alloys at 20°C, using an effective charge of 2.5 for aluminum. In terms of valence, Linde&apos;s equation becomes ?P= {K2 + K1 (Z8 -Za)2} A where K1 and K2 are coefficients, A is atomic percent solute, Z, is valence of solvent, and Zß, is valence of solute. Plots of these data for copper, silver, gold, and aluminum alloys are shown in Fig. 1. The values of K1 and K2 are constant for a given chemical period (P), but vary from period to period. The value of K, increases irregularly with increasing difference between the period of the solvent and solute element (AP), being zero when AP is zero. The value of K, appears to have no obvious periodic relationship. All factors other than valence that affect resistivity are gathered in these coefficients. Because of the nature of the coefficients, Eq. 1 is of limited use in estimating the effects of solute additions on resistivity unless a large amount of experimental data are already available on the systems involved. It is the purpose of the first part of this report to investigate the factors that may be included in the coefficients of Linde&apos;s equation. On this basis, it is hoped that the relative effects of solute additions on resistivity can be better estimated from basic data, leading to a more convenient alloy design procedure. It is well 10,11 that phenomena that decrease the perfection of the periodic field in an atomic lattice, such as the introduction of a solute atom or strain due to deformation, will also increase the electrical resistivity. Thus, in an effort to relate changes in electrical resistivity to alloy composition, it appears appropriate to consider the atomic characteristics related to solution and strain hardening

Jan 1, 1955