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By E. S. Machlin, Morris Cohen

GRENINGER and Troiano' were the first to establish the fact that the habit planes of mar-tensitic products are usually planes of high indices. In steels containing 0.55 to 1.4 pct C, the habit plane indices are {225}A.* In steels with more than 1.5 pct C and in Fe-Ni alloys, the indices are {259In. The presence of both habits in certain alloy steels has been reported recently." Several investigators"-" have subsequently attempted to provide an understanding of these complex habit relations. Bowles'6 work is the most recent and the most successful. Like Greninger and Troiano, Bowles concluded that the transformation occurs in two steps, the first, a strain (or displacement) that is homogeneous throughout the volume of the martensitic plate, while the second is a strain that is homogeneous only within relatively small portions of the martensitic plate. The first strain yields the measured tilt of the specimen surface, but does not produce the final martensitic structure. This and the correct lattice orientations are achieved by the second strain. Bowles also reasoned that each strain could be described by the motion of a plane of no rotation and no distortion (hereinafter called the invariant plane) in a direction not necessarily contained in the plane.** In applying these considerations to steels with {225}a habits, Bowles found that the habit plane coincided with the invariant plane of the first strain, a result which signified that the atoms move along certain paths during the transformation. Whether this correlation results from the existence of some sort of a plate nucleus6 lying along the invariant plane of the first strain, or whether the invariant plane primarily defines the preferred directions of propagation of the first strain, will be discussed in a later section. There are two obstacles to the general acceptance of Bowles' treatment: 1—it has not been shown that elements of his double-strain analysis are unique, and 2—it is not known whether his treatment applies to transformations yielding the {2591A habit. Unless these two questions are resolved, the correlation between the habit and invariant planes in the {225}A systems might be regarded as coincidental. Experimental Procedure Using a 70 pct Fe-30 pct Ni alloy as an example of a {2591A habit system, preliminary attempts were made to obtain a double-strain solution based on a Nishiyamax** set of orientation relations and on a Greninger-Troianot set, adopting the stereographic technique described by Bowles" who used the Kurd-jumow-Sachstt set in connection with the {225}A habit. These attempts were unsuccessful because the method is essentially one of trial and error and requires either exceedingly good luck or a prior knowledge of the results being sought. Consequently it was decided to measure independently the strain associated with the formation of a martensitic plate as well as the habit-plane indices of the particular plate. By means of matrix algebra, the measured strain was applied to the austenite lattice, whose orientation with respect to the strain was determined, in order to ascertain whether the resultant structure would have the lattice of martensite. This was not found to be the case, and hence it was assumed that the measured strain was the first of two Bowles-type strains, characterized by the motion of an invariant plane. A solution of this displacement was obtained in terms of the invariant-plane indices and the direction of motion of the atoms. Then the second strain

Jan 1, 1952

By C. McCulloch

OPEN-PIT mining of coal is relatively a recent innovation; men still active in the industry can trace its development. Re- viewing the growth of operations from the original horse-drawn scrapers, through the various stages of power equipment to the huge strip- ping shovels of today, one also notes changes in the methods of what the coal man calls preparation at the face. We really should not call it face preparation because, in contrast to underground mining, a face does not exist in strip mining. Further, preparation of the coal for market at the loading point has already, in but a few years, become largely of historic interest only and modern mines as well as old mines recently modernized rely almost entirely on separate and elaborate preparation plants to produce marketable coal. This practice was not voluntarily adopted by the producer but was forced upon him by the inadequacy of previous

Jan 1, 1939

By H. Larson, J. Chipman

The ferrous and ferric oxide concentrations of slags, expressed as j = Fe+++/(Fe+++ + Fe++), have been established through gas-slag equilibrium at 1550°C in a range of oxygen pressure of 10-I to 10-9 equilibriumatm. The value of j is increased by basic additions (BaO, CaO, MgO, MnO) and decreased by acidic oxides (SiO2 and TiO2). Oxygen pressure is shown graphically as a function of composition for slags which are analogous to those at the slag-gas interface of the open hearth furnace. THE progress which has been made in recent years in understanding the chemistry of metallurgical slags has been based largely on studies of slag-metal and slag-gas equilibria. There is a considerable body of knowledge which is applicable to reactions occurring at the slag-metal interface in open hearth steelmaking. There is little information concerning reactions of the slag with the furnace atmosphere and hence little basis for an understanding of the transfer of oxygen, sulphur, or hydrogen between gas and slag. The oxygen pressure of the open hearth atmosphere is normally of the order of 10-1 to 10-3 atm which differs by several orders of magnitude from that of about 10" atm at the slag-metal interface. The chemical properties of the slag, for example, the ratio of ferric to ferrous iron and the ability of the slag to hold sulphur in solution, are greatly affected by changes in oxygen pressure. This investigation was undertaken to enlarge our knowledge of the effect of oxygen Pressure on steel-making slags. Using air or controlled mixtures of CO a CO2 a range of oxygen Pressures from 10.' to 10.' was covered. Review of the Literature There are only a few references in the literature which pertain directly to this investigation. The most important is that of Darken and Gurry1,2 on the system iron-oxygen. This work included the determination of the phase diagram of the system and also a study of the field of homogeneous melts and their oxygen pressures. Their apparatus and procedure were very similar to that used in this study. Iron oxide was melted in a platinum crucible under an atmosphere of CO2:CO, CO2:H2, H2O, CO2, air or O2 depending upon the partial pressure of oxygen desired. After equilibrium was reached, the sample was quenched and analyzed for ferrous and ferric oxide. By appropriate calculations these authors were able to determine the oxygen and iron activities in the various slags, heats of formation of the oxides of iron, and heats of solution of iron and oxygen in the liquid slags. In a subsequent paper' the same authors made a less thorough investigation of the effects of additions of lime and manganese oxide on the composition of iron oxide melts. Only a few experiments were made and those in a narrower range of temperature and oxygen pressure. Darken' has investigated the fusion temperature of iron oxide in contact with silica under various atmospheres. He found that the temperature changes from 1120° to 1447°C as the gas composition changes from CO2/CO equal to 20.8 to pure oxygen. A comprehensive paper by White" predates the work of Darken and Gurry. The decomposition of ferric oxide into oxygen and lower oxides of iron was studied from 1000° to 1650°C and under oxygen pressures from 2 to 76 cm of mercury. The effect of

Jan 1, 1954

By M. Garfinkle, W. D. Klopp, W. R. Witzke

The tensile properties of binary W-Re alloys containing up to 33 at. pct Re were determined at temperatures from 78" to 3630°F. Elongations as high as 260 pct were observed in electron-beam-melted tungsten containing 23 at. pct Re when tensile-tested at 3630°F after a 1-hr anneal at 3090°F. All alloys tested under these conditions with rhenium contents between 20 and 28 at. pct exhibited elongations of at least 200 pct. These alloys also showed enhanced grain growth rates. The values of strain-rate sensitivity ranged between 0.2 and 0.3 for the alloys exhibiting high elongations. Houlezler, for swaged alloys tested just above the re-crystallization temperature, strain-rate sensitivities as high as 0.8 were observed. The high-temperature strengths of the high-rhenium-content alloys were also less than those of alloys with intermediate rhenium contents. ALLOYING with rhenium has two distinct effects on the mechanical properties of tungsten. One effect occurs in dilute solid solutions and is most clearly seen in the lowering of the hardness and of the ductile-brittle transition temperature at about 5 at. pct Re.1-3 The second effect occurs in the concentrated solid solution at about 25 at. pct Re, and is characterized by twinning and a larger decrease in the ductile-brittle transition temperature. An aspect of the high-rhenium-content alloy which has received little attention is the higher-than-usual tensile ductility at 3500°F.3 Anomalous high ductility has been observed in several other alloy systems. usually associated with a phase transformation or a solid-solubility limit.4'5 The phenomenon is now commonly termed superplasticity. High-strain-rate sensitivities6 and grain boundary sliding7 have been reported for materials that undergo superplastic deformation. Also, it has been found that superplastic materials usually have a very fine grain structure (less than 10 pm).8 and it has been proposedg that such a structure alone is sufficient for superplasticity. The purpose of the present study was to further characterize the high-temperature tensile properties of W-Re alloys to determine the conditions under which they might be superplastic. Tensile and selected strain-rate sensitivity tests were conducted on alloys containing 0 to 33.3 at. pct Re at temperatures from 78" to 3630°F. Grain-growth rates were also determined on most alloys at 3630°F. Fig. 1 indicates the compositions evaluated and their locations relative to the solvus line in the tungsten-rich end of the W-Re phase diagram. Twelve binary W-Re alloys containing up to 33.3 at pct Re were double electron-beam-melted and subsequently fabricated to 0.3-in. rod by extrusion and swaging. The starting materials were commercial powders of tungsten and rhenium with impurity levels as listed in Table I. The various blended W-Re compositions were hydrostatically pressed at 70 ksi. The pressed bars were drip-melted into 1.5-in.-diam ingots and then remelted into 2-in.-diam ingots at a chamber pressure of 10~5 torr. The ingots were canned in molybdenum and extruded to round bar at a reduction ratio of 6:l. The alloy extrusions were swaged to about an 80 pct reduction at 2100" to 2900°F. Buttonhead tensile specimens with a reduced section diameter of 0.16 in. and a gage length of 1.0 in. were centerless-ground from the swaged bars

Jan 1, 1970

By P. W. Shimer

The purpose of this note is to call attention to a source of error in the determination of graphitic carbon, made by the usual method of solution in hydrochloric acid. Although the method is tedious, because of the necessary treatment of the separated carbon with caustic potassa, alcohol and ether, the text-books seem to give it preference; and it is, perhaps, used more generally than the method of solution in dilute nitric acid. Solution in hydrochloric acid usually gives higher graphitic-carbon results than solution in nitric acid, and many, therefore, consider it more trustworthy, the inference being that the lower results obtained by nitric acid are due to the loss of some of the finely-divided graphite by reason of the oxi-

Jan 1, 1896

By Ralph H. Sweetser

When a furnace-manager is '(blowing in," he generally has no time to consider the composition of the waste gas, and does not bother with it, except to take care that he does not get " gassed." Moreover, the analysis of the gases while the wood is still burning has not much to do with the economy of the normal working of the furnace; yet, on account of the deadly effects of the " blowing-in " gas when inhaled, and of its high explosive qualities, it is interesting to know its composition. In the Transactions there is no record of the analysis of the gas during an up-to-date " blowing-in." Even in Mr. Whiting's admirable paper (Trans., xx., 280) the reported analyses did

Jan 1, 1899

By Charles Becker

THE practice of drying phosphate in Florida is as old as the industry, which began a little more than half a century ago. The methods, however, have changed considerably. At first, the natural process of exposure to the sun and air was used, later supplemented by wood fires beneath open-air stationary dry kilns and drying towers of various designs. It was not until the early nineties that rotary driers came into use, and at first they were of very small design and fired with wood. As the industry grew and tonnage increased, so likewise grew the number and size of rotary driers, until today the largest installations are 6 ft. up to 7 ft. 6 in. in diameter, and 55 to 60 ft. long, fired with crude oil. The reasons for drying phosphate rock are: (1) to eliminate freight on water in the shipment and (2) to facilitate the good grinding qualities required by the buyers in their acidulation. Phosphate pebbles vary materially in natural characteristics and each property has a direct bearing on the processing. In making comparisons of cost and operating conditions, the following are usually taken into consideration: 1. The hard dense pebbles, which contain very little interior moisture and 6 to 8 per cent total moisture, usually produced from the low-grade deposits. 2. The lighter, porous pebbles, which contain 4 to 5 per cent interior moisture and a total moisture ranging from 9 to 15 per cent. 3. The product of recovery operations using oily reagents, containing from 15 to 25 per cent moisture. 4. The size of the pebbles. Usually the plus 5-mesh material is considered as "coarse rock"; the minus 5-mesh plus 24-mesh is "fine rock," and the minute particles below 24 mesh are called "concentrate." 5. The amount of moisture allowed in the dried product. The practice is generally to dry down to 1.5 to 2 per cent moisture. There is, however, an actual range in guarantee of from 1 per cent maximum to 3 per cent maximum.

Jan 1, 1936

By William P. Blake

The metallic element Nickel, discovered by Cronstedt the mineralogist, in the year 1751, as a peculiar metal in kupfer-nickel, remained for a long time comparatively unknown in its true charac-

Jan 1, 1883

By Walter Scott

THE removal of lead by fire refining methods from copper of electrolytic quality is growing in importance. Particularly is this true of the refining of secondary copper and copper cathodes obtained from electrolytic cells where lead is used as the anode material, as in the electrolysis of ore-leaching solutions and foul electrolyte. When investigating the removal of small amounts of lead from molten copper in a reverberatory furnace during the refining of secondary copper of otherwise electrolytic copper quality,1 it was found necessary first to FIG. 1.-SAMPLING DEVICE. know something about the distribution of the lead throughout the bath. The authors believe that it is not generally known how small amounts of lead as an impurity are distributed in a molten copper bath; that is, whether the lead is concentrated at the bottom or at the top, or whether it occurs more or less uniformly throughout the bath. The data contained in this report may help, therefore, in the development of a satis-factory fire refining method for the removal of this obstinate element from a molten copper bath.

Jan 1, 1930

By Charles Janin

The first successful bucket-elevator dredge to operate in California was put in comnlisvion wt Oroville in March, 1898. There had been numerous previous attempts at dredging, but noue of the earlier boats proved a success. The gold-miners in California earl3 conceived the idea of a machine to dig gravel from the beds and bars of auriferous streams that were inaccessible by the methods then employed, and it was only a few months after the discovery of gold in California that such a machine was Shipped around Cape Horn from New York to San Francisco. Thij was, however, but the forerunner of many failures in gold-dredging, and was soon at the bottoni of the Sacramento river. During succeeding years many other unsuccessful attempts mere made, and it was not until 1897 that a dredge of the single-lift bucket-elevator type mas floated on the Yuba river. This dredge was built by the Risdon Iron Works for 12. H. Postlethwaite, and would probably have been a success if it had been operated on some of the rich Ororille ground

Jan 1, 1912

By Henry N. Toler

Oil and gas development in Mississippi during 1936 was about the same as during the past three or four years, with less drilling activity in the proven fields; although at the end of the year there was a decided increase in interest and activity. Jackson Gas Field Six wells were drilled in the Jackson gas field, three of which were producers and three dry holes. The gas production for 1936 was 12,968,-000,000 cu. ft., which is 2,500,000,000 cu. ft. more than for any previous year. The total gas production from the field to the end of 1936 has been 58,092,000,000 cubic feet. Thirteen producing gas wells were abandoned during the year because of encroachment of salt water. At present there are 99 producing gas wells in the field. The three oil wells on the edge of the field, which had been producing, were not produccd during 1936, although they are still capable of making some oil with much salt water. The rock pressure at the end of the year was 930 lb., which is a decline of 80 Ib. since the discovery of the field. In March of 1936, the State Legislature appropriated $115,000 to be used by the State Mineral Lease Commission in drilling some gas wells

Jan 1, 1937

By Albert Wright

VEINS of asphalt fill and seal vertical fault fissures at the surface of a large domal structure near Bejucal, Havana Province (about 19 miles south of Havana), so this structure was chosen, by Barnabas Bryan, for the drilling of a well on the theory that oil had risen from below the Cretaceous and had entered the porous sands of the Upper Cretaceous, which outcrop in three places within a radius of 12 miles. The asphalt in these fault fissures, he contended, had sealed them and thereby prevented further dissipation of the oil. Furthermore, he found, in the asphalt, specimens of sand and lime that were indications of its upward migratory character. Ralph Arnold, who discovered the Upper Cretaceous sand saturated with oil in the outcrop near Mariel, in Pinar del Rio Province, has compared the Bejucal structure with the Santa Maria field in California. The surface rock of the structure is Oligocene limestone and shales, thin, bedded and well stratified. This formation has, heretofore, been assigned to the Eocene with a thickness of 3000 ft. and locally called the Nazareno formation. Paleontologic examination of well cuttings, however, has disclosed Oligocene fossils at a depth of 1142 ft. and Upper Cretaceous fossils at a depth of 1541 ft., leaving approximately 400 ft. of very parenthetical Eocene. Whether there is any Eocene in this structure has not been determined.

Jan 3, 1925

By V. H. Wilhelm

In contrast with the previous year's activity, the California oil industry for 1938 showed a decrease in drilling, market demand, and discovery of new oil reserves, although there was an increase in oil production. Although additions to reserves from new fields and extensions were less than withdrawals during the year, reappraisals of discoveries in 1937 added to new discoreries during 1938 amounted to over 300,000,000 bbl. The following comparative statement shows the important changes in various phases of the industry: Throughout the year the storage situation became progressively more acute, owing principally to less Pacific foreign demand, and increased potential from drilling the newly discovered fields and pools (Fig. 1). California storage increased approximately 32,000,000 bbl. during 1938, most of which (approximately 18,000,000 bbl.) was heavy crude and residuum. The market demand for the year was around 600,000 bbl. per day. Because of the trend toward Diesel power for heavy transportation, the non-gasoline-bearing crudes arc fast becoming a drug on the market. New discoveries were instrumental in increasing the potential production of the state from 1,076,000 bbl. per day in January to an all-time high of 1,420,000 bbl. per day at the close of the year; although the indicated reserves of these new discoveries were not equal to the yearly withdrawal of 249,000,000 bbl. As of the end of 1938, the state was voluntarily curtailed about 58 per cent. As a result of prospecting during the year, six new fields were discovered, three fields were extended, and deeper zones were reached in five of the older fields.

Jan 1, 1939

By V. H. Wilhelm

In contrast with the previous year's activity, the California oil industry for 1938 showed a decrease in drilling, market demand, and discovery of new oil reserves, although there was an increase in oil production. Although additions to reserves from new fields and extensions were less than withdrawals during the year, reappraisals of discoveries in 1937 added to new discoreries during 1938 amounted to over 300,000,000 bbl. The following comparative statement shows the important changes in various phases of the industry: Throughout the year the storage situation became progressively more acute, owing principally to less Pacific foreign demand, and increased potential from drilling the newly discovered fields and pools (Fig. 1). California storage increased approximately 32,000,000 bbl. during 1938, most of which (approximately 18,000,000 bbl.) was heavy crude and residuum. The market demand for the year was around 600,000 bbl. per day. Because of the trend toward Diesel power for heavy transportation, the non-gasoline-bearing crudes arc fast becoming a drug on the market. New discoveries were instrumental in increasing the potential production of the state from 1,076,000 bbl. per day in January to an all-time high of 1,420,000 bbl. per day at the close of the year; although the indicated reserves of these new discoveries were not equal to the yearly withdrawal of 249,000,000 bbl. As of the end of 1938, the state was voluntarily curtailed about 58 per cent. As a result of prospecting during the year, six new fields were discovered, three fields were extended, and deeper zones were reached in five of the older fields.

Jan 1, 1939

By G. L. Oldright

Nearly all of the present schemes for treating complex (i. e. lead-silver-zinc-copper) ores are based on the idea that lead holds, and will hold for some time, the strongest economic place from the viewpoint of supply and demand of all the non-ferrous metals. Copper, it is thought, will come back to its own when European affairs are stabilized, although at that time competition from Chile, Peru, and Katanga, in particular, will be more severe than in pre-war days. The future for silver and for zinc is uncertain. New uses are developing for zinc, and the market has remained better than many expected, but the stabilization of world markets will bring in foreign competition instead of relief. The cost of producing zinc from simple zinc ores, by the retort process, will, from the nature of the labor required and the increasing cost of fuel, increase steadily. As a result, the small producers of purely zinc ores around Joplin are shutting down their mines, even with a good market price for zinc; on the other hand, the producer of lead from complex ores, in the Rocky Mountain states, is confident of a profit from the sale of his lead, and is seeking means to make the zinc in his ore pay some part of the cost of treatment. However, the tonnage costs for mining and ore dressing are much higher in the Rocky Mountain states, as may be seen by comparing tax-return statements from the various states. Even before the recent drop in the price of silver, many mines were operating on a very slender margin of profit; labor and supplies cost more. Mining at greater depth has shown most orebodies to grow increasingly more complex, so that improvements in mining and ore-dressing practice have not been sufficient to compensate for the additional expense involved in beneficiating these ores. The smelters have bad to meet the same general economic situation, so they can only give

Jan 1, 1924

By Charles Becker

THE practice of drying phosphate in Florida is as old as the industry, which began a little more than half a century ago. The methods, however, have changed considerably. At first, the natural process of exposure to the sun and air was used, later supplemented by wood fires beneath open-air stationary dry kilns and drying towers of various designs. It was not until the early nineties that rotary driers came into use, and at first they were of very small design and fired with wood. As the industry grew and tonnage increased, so likewise grew the number and size of rotary driers, until today the largest installations are 6 ft. up to 7 ft. 6 in. in diameter, and 55 to 60 ft. long, fired with crude oil. The reasons for drying phosphate rock are: (1) to eliminate freight on water in the shipment and (2) to facilitate the good grinding qualities required by the buyers in their acidulation. Phosphate pebbles vary materially in natural characteristics and each property has a direct bearing on the processing. In making comparisons of cost and operating conditions, the following are usually taken into consideration: 1. The hard dense pebbles, which contain very little interior moisture and 6 to 8 per cent total moisture, usually produced from the low-grade deposits. 2. The lighter, porous pebbles, which contain 4 to 5 per cent interior moisture and a total moisture ranging from 9 to 15 per cent. 3. The product of recovery operations using oily reagents, containing from 15 to 25 per cent moisture. 4. The size of the pebbles. Usually the plus 5-mesh material is considered as "coarse rock"; the minus 5-mesh plus 24-mesh is "fine rock," and the minute particles below 24 mesh are called "concentrate." 5. The amount of moisture allowed in the dried product. The practice is generally to dry down to 1.5 to 2 per cent moisture. There is, however, an actual range in guarantee of from 1 per cent maximum to 3 per cent maximum.

Jan 1, 1936

By Horace Knerr

The term. "high-yield-strength," used in the title of Dr. Gillett's paper (p. 40) is obviously relative. His discussion is limited to improved steels intended to compete with the low-cost, low-carbon, hot-rolled, sheet and plate steels of commerce made and used on a tonnage basis, without heat-treatment. In his list of about three dozen steels, only three have a yield strength of 70,000 lb. per sq. in., or over. Double such values are not uncommon in aircraft steels. Dr. Jeffries (p. 21) refers to "light-weight metals," obviously meaning strong alloys of low specific gravity; namely, aluminum alloys of the duralumin type and certain magnesium alloys. In a structural material, "lightness" is determined by two factors, strength and specific gravity. They must always be considered jointly. The basis of comparison is a strength-weight ratio, obtained by dividing the desired strength value, such as tensile strength, yield strength, or endurance limit, by weight per unit of volume, such as specific gravity or pounds per cubic inch1. For example, aluminum is a heavy metal, structurally, unless alloyed and heat-treated to give it high strength. When the strength of a structural metal is raised by heat-treatment or by cold-work, its specific gravity is not appreciably changed, but it is made lighter in direct proportion to the increase in strength because less of it will be required to carry the load. The lightness of the finished structure of adequate strength is the real point of interest. This structure must not only carry designed load, but "stand the gaff" of service, which includes the effects of accidental overload, fatigue, corrosion, loosening of joints, and so forth. Neither Dr. Gillett nor Dr. Jeffries mentions the true "lightest material of construction," which is alloy steel, tubular in form (Fig. 1), assembled by welding and heat-treated to a yield strength in excess of 150,000 lb. per sq. inch.

Jan 1, 1936

By C. E. Birchenall

DaVIES and Richardson1 have measured composition changes for Mn1-Owith variation in the equilibrium partial pressure of oxygen at 1500°, 1575°, and 1650°C, where 6 is the deviation from the simple stoichiometric ratio. No trend in this relationship with temperature was observed, so these remarks apply to the whole temperature range. The experimental values and their spread are shown by the bounded straight-line segments in the figure. Davies and Richardson assume that the stoichiometric oxide shows Frenkel disorder, given by the equation Mn2+Mn2+ + Mn" [1] where Mn2+ is a normal lattice ion which moves into an interstitial site (Mni2+) leaving a vacancy (Mn,"). The superscript dashes indicate that there is an excess charge on the anions surrounding the vacancy. Schottky disorder, in which a perfect crystal acquires equal numbers of cation and anion (Ov") vacancies according to leads to equations of exactly the same form in the analysis below. In view of the neutron diffraction results of Roth,2 which shows extensive Frenkel disorder in Fe1-o, Eq. [I] seems more appropriate. The deviations from stoichiometric composition, MnO, result from the addition of oxygen according to In effect Davies and Richardson ignore the variation of Mn3+in constructing equilibrium constants. This approximation might not appear to be very serious if the excess positive charges are really free posi- tive holes (P+) and if the intrinsic conductivity is high as a result of the reaction where e- is a conducting electron. However, the calculations of Buessem and Butler3 indicate that the partition functions of the free charges make a large contribution to the equilibrium constant, and this approximation would not be a desirable one. Furthermore, Morin4 shows that the positive holes are probably localized in MnO and therefore are described better by the mass action principle than by a degenerate gas model. Davies and Richardson's considerations require that activity corrections be applied beyond a 6 value of about 0.005. It is proposed to show here that the dissociation pressure curve can be calculated reasonably well over the whole composition range studied without activity corrections by choosing appropriate equilibrium constants for reactions 1 and 2. As stoichiometric composition The mass action constant, Ks, for reaction [I.] and the equilibrium constant, K,, for reaction [2] are given by where the concentrations which do not change significantly have been absorbed into the constants. The brackets denote concentrations. The deviation from stoichometric composition is given by gardless of [Mni2 ]. Substituting Eq. [7] in [6]

Jan 1, 1961

By H. Bloom, H. E. Hawkes

STREAMS and rivers are the principal channels into which the weathering products of rocks and their contained ores are funneled. The inorganic load of a stream system is a crude sample of all the earth materials in the drainage basin of the stream, and the heavy mineral assemblage of sediments is one of the oldest and most successful guides to certain kinds of bedrock ore in unexplored terrain. Early application of this method was made possible by the ease of separation and identification of heavy minerals in the field with the simplest equipment. Water analysis for traces of base metals became a practical possibility about eight years ago with the development of rapid chemical tests that could be carried out at the field site.' , Since that time the water method has been widely used in mineral reconnaissance, and a substantial number of discoveries have been reported. Here again, the techniques developed for this work were relatively simple and could be performed easily at the field site. Sediment analysis by chemical methods, as distinguished from mineralogical, has received less at- tention. Some experimental work was done by Lovering and others," but to the authors' knowledge, chemical analysis of sediment samples has not been used in routine exploration programs until very recently. In spite of the obvious promise of this method, it was not pursued vigorously because of the lack of a simple and portable chemical test that could be used conveniently at the field site or in a field camp. Procedures that had been developed for trace analysis of soils all called for a rigorous chemical attack with hot acids—tests more conveniently applied in processing large volumes of routine soil samples at an established field headquarters. Recently an extremely rapid and simple test was developed by Bloom.4,5 The extractant used in this procedure is a cold solution of ammonium citrate. Elements measured are the heavy metals, principally zinc, lead, and copper. This method differs from the established procedures for soil analysis in that it measures only a small fraction, about 5 pct, of the total metal content of the sample. It has been found, however, that the significant pattern of metals in the sediments of streams below a base-metal deposit can be brought out as well and sometimes better by this simple cold-extraction procedure than by the more tedious methods requiring hot acids. To understand fully the significance of the relation between the readily extractable and the total

Jan 1, 1957

By Harold Markus, Gerhard Derge, Arthur Grobe

THE high corrosion resistance possessed by tin under most circumstances, combined with its generally satisfactory appearance and useful physical properties, has led to many and varied uses for the metal. These uses have been partly limited by the fact that tin is an expensive metal, therefore many applications have been developed in which tin has been employed in combination with lead, either by coating, as in tin-lined collapsible tubes, or by the formation of alloys containing various proportions of tin-rich and lead-rich phases, as terne plate. A detailed knowledge of the corrosion characteristics of the tin-lead couple therefore is of general interest and has become specially important at the present time, when every effort is being made to conserve tin as much as possible. The present study has been limited to carbonate solutions with a pH range from 8.4 to 11.2 so that the results may be related to earlier work on the corrosion of tin and its alloys.1-3,6 In these papers, the effects of a number of anion and cation additions to these solutions have been observed. APPARATUS AND METHOD The electrodes for the corrosion cell were cut from rolled sheet about 1/16 in. thick. The length of all specimens was held constant at 7 in., while the width was varied from ½ to 2 in. These electrodes were fastened to brass electrode supports, which were attached to rubber stoppers fitting into tall-type one-liter Pyrex beakers that contained the electrolyte. The lead electrodes were prepared from Omaha pig* and the tin was rolled from a slab of Chempur.† After cutting to size, the sheets were polished with No. I emery paper and cleaned with carbon tetrachloride. The edges, back and upper parts of the specimen were coated with a synthetic lacquer, which was supplemented with beeswax for the lead electrodes. The binding posts were coated with beeswax after the electrodes had been clamped. The pH of the electrolyte was controlled by adjusting the ratio of carbonate to bicarbonate. Approximately 600 ml. of electrolyte was used in each beaker. The entire assembly was placed in an oil bath thermostatically adjusted to operate at 30°C. ± 0.1°. Potentials were measured against a saturated calomel electrode connected to the cell by an agar-agar salt bridge. The carbonate solution used in the salt bridge was the same as that used in the corrosion cell. Currents were measured with a milliam-

Jan 1, 1942