Search Documents

By David Schlain

"IntroductionThe purpose of this investigation was to study the characteristics of the high-acid electrolytic manganese cell with the idea of fitting it into one of the flow sheets being worked out by the Metallurgical Division of the Bureau of Mines for the recovery of manganese from low-grade domestic ores.In construction, the high-acid cell 3/ differs from the low-acid type in that the cathode and anode compartments are separated by a diaphragm of relatively low porosity, such as alundum. This is necessary because in the high-acid cell the two electrolytes are circulated separately. The anolyte is 15 to 30 percent H2SO4. The catholyte consists of a solution of ammonium sulfate and manganese sulfate with a OH of 4 to 3. The only mixing of electrolytes is that resulting from flow through the diaphragms. In the low-acid cell the two electrolytes are not circulated separately and do not differ so widely in hydrogen-ion concentration. Hence, the canvas diaphragm is sufficient.During operation of the cell, manganese is deposited on the cathode, and sulfuric acid is produced in the anode compartments. Various other reactions take place in the cell. There is considerable decomposition of water; hydrogen is evolved at the cathode, and oxygen is liberated at the anode. When lead anodes are used, some hydrated oxides of manganese are formed at the anodes. The quantity of oxides formed is not as great as it is in the low-acid cell, because fewer Mn++ reach the vicinity of the anodes."

Jul 1, 1942

By A. R. T. Denues, A. P. Rowles

"INTRODUCTION Summarized data developed by J. E. Crawshaw and E.J. Murphy, 4/of the Explosives Division of the Bureau of Mines, suggesting marked variations in oxygen condition in three permissible explosives, have been reported 5/. Such variation is of interest in other work, it having been shown, for example, that the oxygen condition may have marked effect upon the products 3/ and the propulsive strength 7/ of explosives. It seemed that a more detailed presentation and more usual statistical analysis of these data might be of considerable general interest and not complemented in the literature.This report presents both the original data developed by Crawshaw and Murphy and the results of a simplified but seemingly acceptable statistical analysis of these data. The logical ground for this analysis might seem somewhat questionable because of the lack of systematic information concerning the extent of errors in the analytical procedure but the data show that there are several cogent and seemingly unequivocal indications of real heterogeneity in the explosives."

Jun 1, 1942

By S. M. Shelton, M. M. Fine, T. L. Johnston

"INTRODUCTION The Bynum property is about 15 miles west of Gadsden and 1 mile north of Walnut Grove, Etowah County, Ala. The ore lies in layers and as irregular masses and pockets in the clay residue from decomposed quartzite and limestone formations to the district.The property has been developed by means of numerous shallow shafts sunk to water level - about 25 foot. Operations are confined to small-scale, selective mining of pockets of high-grade ore. The ore is marketed directly, without beneficiation. The property does not yield a large amount of manganese ores. No estimates of reserve ore tonnages are available.A 206-pound sample was furnished for test. It was taken at random from a stock rile estimated to contain 130 tons of ore. The sample con¬sisted of a mixture of manganese oxides, iron oxides, and siliceous fragments in clay. The manganese occurred largely as soft, unconsolidated pyrolusite and wad. Some hard, crystalline pieces of psilomelane were distributed through the soft material. Small amounts of iron oxides were associated with the manganese oxides. Chert, quartzite, and clay comprised the gangue minerals.Dry analysis of the sample was as follows: 36.0 percent manganese, 6.1 percent iron, 2: .0 percent silica, 1.5 percent calcium carbonate, 0.36 percent phosphorus, 3.0 percent alumina, 2.2 percent barium, and 0.31 percent zinc."

May 1, 1942

By James T. McCartney, Joseph D. Davis

For more than 10 years coke-oven technologists have been investigating the expanding properties of coal on a scale larger than that afforded by laboratory test tubes. Koppers 4/ was among the first to realize that coals can not be differentiated satisfactorily with respect to expansion in coke ovens by the simpler test-tube methods; in his first method 80 grains of fine coal were coked in a cylinder heated from the bottom, so that the zone of fusion (plastic layer) advanced from the bottom to the top. The scale of test was too small; it has been modified by other investigators, but without significant improvement in practical application of the results. Somewhat later Koppers and Jendne 5/ experimented with a small-scale coke even, one wall of which was movable, in which the layer-coking in a coke oven could be simulated closely. This oven was heated from both sides. Their results with this oven showed a peak in the time-pressure curves near the end of the coking, period when the two plastic layers, advancing from opposite walls, meet. They also found that although the smaller oven was heated from one side only and did not show the Pressure peak characteristic of two-sided heating, it still gave results entirely too high. Russell built an oven similar to the movable-wall oven of Koppers and Jenkner and compared results obtained in it on Beckley expanding coal with these obtained on the some coal in the Altieri 7/ small-scale apparatus. Both tests were conducted at the same constant pressure, but heating was from two sides in Russell's oven and from one side in the Altieri tester. Russell found that the two types of test gave comparable results under constant pressure conditions even though the heating procedures were quite different. He showed later, however, that a "borderline" coal 8/ that contracted in the Altieri tester at constant pressure developed a peak pressure of 4 pounds per square inch in the movable-wall oven heated from both sides at constant volume. He concluded from this that testing at constant volume gave results more accurately indicative of dangerous expansion tendencies than those at constant pressure. He also found that heating from both sides in this oven gave higher pressure than heating from one side only.

May 1, 1942

By E. J. Murphy, John C. Holtz

"INTRODUCTION Toxic gases in the products from the detonation of explosives are one of the hazards in blasting underground. Investigations by the Bureau of Mines 4/5/ have shown that the oxygen balance of the explosive is an important factor in the control of toxic gases. This balance is considered in determining the composition of modern metal-mining explosives for blasting underground, and application of the concept has reduced the volume of toxic gases generated.The chemical nature of the material being blasted also influences the composition of the toxic gases produced. Under some conditions of blasting in massive pryrite, unsafe concentrations of sulfur dioxide and hydrogen sulfide have been found.Experiments with the O-J apparatus 8/ have shown that there is an increase in the volume of carbon monoxide in the gaseous products when permissible explosives are detonated in contact with coal dust. Thus, reactive materials of a reducing nature adjacent to explosives loaded in drill holes may decrease the effective oxygen balance of the explosive and cause the volume of toxic gases to increase.Several blasting accessories of reducing nature have been introduced recently for use in coal or metal mines or tunnels. In practice these are loaded adjacent to the explosive where conditions favor reaction with the products of detonation. The effects of this loading on the gaseous products obtained from the shot are indicated in this report. Broad consideration was not given the efficiency, usefulness, or over-all safety of these devices, but the practical significance of the hazard resulting from increased volume of carbon monoxide is discussed."

May 1, 1942

By H. H. Schrenk, Carlton E. Brown

"The purpose of this paper are (1) to present a broad picture of the recognized methods of measuring the various forms of atmospheric pollution; (2) to evaluate the significance of such measurements; and (3) to suggest suitable methods for obtaining comparative information on the concentration of contaminants in city air.The atmosphere (the gaseous envelope surrounding the earth) consists of a mixture of gases. These gases and their usual proportions are:4/The volume of water vapor in the atmosphere ranges from almost zero (in very cold weather) to about 5 percent arid averages about 1.2 percent.Strictly speaking, any other substance in the atmosphere or an excess of any of the substances mentioned (with the possible exception of water) is a contaminant. Needless to say, there are many contaminants in the atmosphere.In accordance with their physical state, contaminants may be classified as gaseous or particulate, and the latter may be classified as solid or liquid matter. Particulate matter, especially when dispersed in some medium such as air or some other gas, sometimes is referred to as dispersoid, and the complete system of gas and dispersoid is referred to as aerosol.All substances on the earth are potential sources of atmospheric contaminants. Combustible materials (particularly fuel for heating and power), sea water, earth or soil, metals, and animals (including man) are some of the important sources of contaminants.Ordinarily gases are produced by chemical processes, whereas dispersoids are produced by both chemical and physical processes. There are two general dispersoid-producing processes: (1) Condensation, in which molecules join to form larger units or particles, and (2) disintegration, in which large units are reduced to the particulate range (which for the purpose of this article may be considered to be from 100 microns, or 1/254 inch, down to molecular size) by such processes as crushing, grinding, abrading, and atomizing.“Condensoid"" is a convenient term for dispersoids formed by condensation, and ""disintegrasoid"" for those formed by disintegration. Solid condensoids are sometimes called ""fume,"" solid disintegrasoids ""dust,"" liquid condensoids ""fog,"" and liquid disintegrasoids ""mist.""5/"

May 1, 1942

By Kenneth Eilerts, Vincent Smith

"INTRODUCTION Knowledge of the Phase relations of fluids produced from combination wells 4/ at the pressures and temperatures characteristic of production from natural reservoirs is essential to efficient recovery and refining practice. An accurate sample of the fluid from such wells may be prepared by mixing (in the proportions of the measured gas:liquid ratio) gas and liquid taken from the separator conditions of steady flow; and physical properties of the sample, at significant pressures and temperatures, may be determined with suitable laboratory apparatus for use in the solution of engineering problems. The results of study of sample so obtained and of mixtures of gas and liquid from the separator combined in other proportions are presented in this report. Attention was given in the study to the relationship between the physical properties of what may be regarded as the constituent materials - the gas and liquid taken from the separator - and the properties of mixtures of these constituents. Data obtained for the complete range of mixture Proportions are expected to provide a reference scale for the study of other combination-well fluids produced at different liquid:gas ratios."

Apr 1, 1942

By J. B. Zadra, S. M. Shelton, R. B. Fisher, M. M. Fine

"INTRODUCTION An extensive test program is in progress by the Bureau of Mines to determine ways and means of recovering ferromanganese ore 5/ from the widespread domestic manganese and manganiferous iron deposits.Samples were received from the Stance property in southwestern Virginia, 12 miles northwest of Stoney Gap, in Bland County.The Stange mine is situated on the crest of Flat Top Mountain and is developed by open-cuts extending over several acres. The manganese deposit occurs in the Oriskany sandstone largely as a replacement of the sandstone, to some extent as breccia filling in the crusted parts of the sandstone, and as veins along joints, and bedding planes.The mine was first worked in 1917 and was operated during the war years. A long period of idleness was followed by intermittent operations in recent years. A small log-washing plant, consisting of a 20-foot log washer, was operated 1-1/4 miles northwest of the mine. The log-washer concentrates were crushed to minus- 1/2 inch and then washed in a second log washer to remove as much of the siliceous sandstone as possible. According to a communication from the operator, the double-washed concentrates were jigged and the jig concentrates marketed without further beneficiation."

Apr 1, 1942

By S. M. Shelton, J. B. Zadea, M. M. Fine, T. L. Johnston

"INTRODUCTION The Mayfield manganese property is about 25 miles south of Van Horn, in Jeff Davis County, Tex. The ore deposit is developed by a large open-cut and a small stope.An 8-ton sample was received for testing; it was taker at random from material on the mine dumps and consisted of a mixture of manganese oxides, barite, and siliceous gangue minerals. The manganese occurred largely as hard, massive, crystalline psilomelane, with a small amount of pyrolusite. The gangue minerals consisted of intermixed iron-stained sand stone, quartzite, chalcedony, calcite, quartz, and barite. Chemical analysis showed 8.9 percent manganese, 3.3 percent iron, 38.4 percent silica, 6.6 percent calcium carbonate, 7.1 percent barium, 3.1 percent alumina, 0.09 percent phosphorus 0.01 tungstic oxide, and less than 0.05 percentAnalysis of selected clean pieces of manganese minerals, free of gangue, showed 48.1 percent manganese end 13.4 percent barium, of which only 0.2 percent was present as barium sulfate. This indicated a limit in concentration. Barium was also present in the gangue as a separate mineral, barite (BaSO4), which has approximately the same specific gravity as the manganese oxide."

Apr 1, 1942

By S. M. Shelton, W. A. Calhoun, M. M. Fine, T. L. Johnston

"INTRODUCTION An extensive test program is in progress by the Bureau of Mines to determine ways and means of recovering ferromanganese-grade ore 6/ from the wide-spread domestic manganese and manganiforous iron deposits. Samples for testing were received from the Interstate Manganese Co. in northeastern Tennessee, 11 miles west of Mountain City and 10 miles southwest of Damascus Va. The ore deposit occurs in the residual material of the Shady dolomite 7/ as an unconsolidated mixture of hard and soft manganese oxides and clay.Numerous tunnels and pits have developed a large reserve of ore in an area of about 15 acres. One pit 250 by 50 by 20 feet is being mined by rower shovels. The ore is hauled to a washing plant for log-washing, hand-sorting, and jigging. Coarse concentrates from the washing plant are marketed without further beneficiation.ACKNOWLEDGMENTSThe authors wish to acknowledge the assistance of R. F. Fisher, who made the roasting and magnetic tests."

Mar 1, 1942

By Gustav Wafe

"INTRODUCTION The discovery in 1901 of ""gusher"" oil production at Spindletop, Tex., Tex., a salt-dome structure, led to exploratory drilling on other known domes and known domes and in areas contiguous to salt domes in the Gulf Coast region of Texas and Louisiana. Early drilling on the flanks of the domal structures disclosed incompetent 3/ shales, which flowed into the hole when attempts were made to drill through them. Often these shales seized the drill pipes and presented with equipment then in use, an insuperable barrier to deeper drilling. The obstructing incompetent shales came to be called ""heaving"" shales by drillers who attempted to drill through them. Formations of this type have hampered the penetration of the drill bit in many area in the Gulf Coast region to such an extent that the drilling of wells through heaving shale has become a major problem."

Mar 1, 1942

By S. M. Shelton, A. L. Engel

"This report presents the results of investigations of ore-testing projects assigned to the Ore-Dressing Section, Metallurgical Division, Bureau of Mines, at the Mississippi Valley Experiment Station, Rolla Mo. During the fiscal year ended June 30, 1941.The manner of approving ore-testing projects has been explained in a previous reports. 4/ The testing procedures likewise have been described. 5/The treatment methods described are based upon laboratory experiments with small amounts of sample and naturally are subject to the inherent, normal, limiting conditions of such procedure. It is not intended to describe treatments in detail, but rather to indicate applicable methods. Local operating conditions, when the laboratory results are applied to plant operations, may require further study. Large-scale pilot-plant tests should be made before commercial operations are begun, so that translation from the experimental stage will yield satisfactory results."

Mar 1, 1942

By J. A. Pile, Virgil Miller, R. G. Peterson, F. B. Petermann

"INTRODUCTION As virtually no published data are available on the sintering of fine, minus-100-mesh, ferrograde manganese ores, it is most opportune to present data on the amenability of various fine ores and mill products to the sintering process. These data cover the sintering or nodulizing of finely crushed, high-grade pyrolusite and rhodochrosite ores, sintering of manganese carbonate flotation concentrate, sintering or nodulizing the calcine from the deleading of a manganese oxide flotation concentrate, and sintering the calcines made in a Herreshoff furnace from the treatment of manganese sulfate products.If finely sized products are to be smelted in the present electric or blast ferromanganese furnaces, they must be sintered or nodulized. The only specification as to the size of the sintered or nodulized product is that it must pass a 6-inch screen and not contain over 1t-1/2 percent minus 20-mesh material. The minimum-maximum size has not been established. Undoubtedly this opti mum size will be set by the ferromanganese industry when ample quantities of manganese oxide sinters have been smelted."

Mar 1, 1942

By W. E. Miller, G. S. Scott, G. W. Jones

"An important activity of the Bureau of Mines is the promotion of safety in mining and industry. In connection with these activities, the Bureau determines the explosion hazards of combustible gases, liquids, and solids and investigates means by which explosions may be eliminated or reduced in violence.The limits of inflammability and ignition temperature of combustible gases, vapors, and solids are of practical importance because such materials can be manufactured, transported, and used with greater safety, provided the range of concentrations and temperatures that cause explosions are known.Many organic compounds, which until a few year ago were merely laboratory curiosities, are now being manufactured in large quantities owing to the national emergency, particularly those chemicals entering into the manufacture of synthetic rubber, a product that is playing a major role in the Government program of national defense. This re Jolt gives results relative to the limits of inflammability of styrene and its ignition temperature in air and oxygen. This combustible liquid is now used extensively in the manufacture of synthetic rubber."

Mar 1, 1942

By S. M. Shelton, W. A. Calhoun, M. M. Fine, T. L. Johnston

"FOREWORDFerrograde manganese ore or its equivalent is essential to the manufacture of every ton of steel produced; although it is well known that there are large deposits of low-grade are in the United States, the production of substantial amounts of ferrograde material from domestic sources presents a problem that becomes more and more critical as the stockpiled ore depleted through inability to procure adequate supplies from foreign sources. Consequently, a program of laboratory,and pilot-plant investigation designed to solve the problem of obtaining a domestic supply of manganese has been undertaken by the Metallurgical Division, Bureau of Mines.This paper is one of a new series that include reports of results obtained in the various investigations conducted under the manganese program. The scope of the program and the organization that was set up to direct and supervise the were discussed in the foreword of the first paper of this series, Report of Investigations 3606 Manganese Investigations. 1. Concentration of Manganese Ores,from the Drum Mountain District, Utah, by S. R. J. D. Vincent, and C. R. Schack. Other reports will be published as the work progresses."

Mar 1, 1942

"These tentative coal mine inspection standards have been prepared as a guide for the Federal inspection of coal mines of the United States. Much time and thought have been spent by various members of the Safety Division in the preparation of thses standards, and it is believed that compliance with them eventually will be possible in most mines. In many instances objections will be raised to them owing to long-established mining customs and practices that are inherently of dubious safety and to a natural inclination to oppose change. In other instances there will be valid objections due to conditions not foreseen at the time these standards were prepared. Or there may be substandard conditions and practices due to original mine layouts that it is not practicable to change during the lifetime of the mine; in such instances it is likely that some effective measures are or can be taken toward lessening hazards.With the rapid change in mining methods some of the standards may become inapplicable and it may be advisable to revise them to meet the new conditions. Therefore, questions regarding these standards and suggestions regarding new standards should be brought to the attention of the supervising engineer of the Coal Mine Inspection Division so that modifications of and additions to these standards may be made from time to time.In many respects these standards exceed the provisions of the various State mining laws, and some may conflict with the laws of some States. In cases of conflict, the intent is not to advocate noncompliance with State laws but to suggest that it may be desirable for the State to reconsider such laws or safety orders.Although an effort has been made to word these standards so that they may be readily understood, nevertheless, a reasonable interpretation should be placed upon them. In fact, in numerous instances the words reasonable"", ""suitable"", and ""properly"" are used in recognition of the fact that reason- and sound judgment enter into the carrying out of the safety endeavor.The policy of the Bureau on some vitally important safety matters in mines is set forth in its published Safety Decisions. These decisions have been consulted and used in the preparation of these standards. These decisions also are now being reexamined by its Mine Safety Board."

Feb 1, 1942

By Raymond D. Sloan

Development and exploration in Oklahoma showed a definite increase in 1941 over 1940 in production, wildcat activity and total well completions. Geological and geophysical work continued and possibly increased slightly in amount. Oklahoma retained third place in the ranking of oil-producing states of the nation, topped only by Texas and California, and followed by Illinois in fourth position. Production averaged 416,800 bbl. daily, a 1.7 per cent increase, as compared with 409,900 bbl. daily for the year 1940. Maintenance of the state's relatively stable producing rate resulted from the discovery of numerous small pools, the recombing of old areas, the establishment of new producing horizons, and the drilling of an increased number of marginal wells. The market for the Mid-Continent crude was strengthened materially to meet the increased demand. Coincident with a deeline in production in Illinois, shipment of Oklahoma-Kansas crude to the eastern points averaged 453,000 bbl. per day, an increase of 49.4 per cent as compared with 1940. The movement south amounted to an average of 42,000 bbl. per day, a loss of 41.7 per cent. Secondary-recovery programs in Oklahoma were given more consideration, operators realizing that in the future many pools would necessarily have to resort to this type of operation. Five permits for water-flooding were issued by the Corporation Commission during the year. These projects were in Rogers, Wagoner and Nowata Counties, in the shallow northeastern area, which has relatively extensive development of this type in the Bartles-ville sand at from 600 to 1000 ft. in depth. Gas repressuring of an individual lease in the 35-year old Glenn pool, Creek County, proved relatively successful, and after a year's operation was extended to cover a much larger area, with several operators participating. More of this type of work is expected in the future; however, it was given an initial setback when the legislative proposal authorizing secondary recovery in the Wilcox zone of Oklahoma's largest pool, the Oklahoma City pool, was pigeonholed by the committee. A continuation of the low discovery rates within the state would possibly lead to a revival of interest in the project. Many pools formerly classified as prorated areas were removed from this classification and transferred into the group of settled production. At the close of the year the issuance of the Federal Conservation Order M-68 and the interrelated Preference Rating Order P-98 caused a sharp decline in drilling operations, which is expected to continue until such operations are stabilized at a lower rate. The ultimate effect of these two orders on discoveries, production and reserves is a matter of speculation and conjecture. During the year, 2110 new wells were drilled, an increase of approximately 18 per cent as compared with the previous year. Of the total, 1235 were oil wells with a combined initial potential of 342,754 bbl. daily, 178 were gas wells with a total

Jan 1, 1942

By William B Price, Ralph W. Bailey

Arsenic, antimony and phosphorus are now used in the brass industry as standard inhibitors in preventing dezincification in condenser tubes. This subject has been thoroughly covered by Barry,l who de- scribed the testing procedure by total immersion of suitable specimens in a I per cent cupric chloride solution at definite temperatures. Effects of dezincification were then determined by loss in tensile strength and elongation of the test specimens after definite periods of immersion. In the crystallography of the chemical elements as tabulated by William Hume-Rothery,2 phosphorus (metallic), arsenic, antimony and bismuth are placed in group V-B and the type of crystal lattice for arsenic, antimony and bismuth is given as rhombohedral. The Metals Handbook3 lists them as 'rhobomhedral hexagonal," with the additional notation that for arsenic this is the ordinary form at 20°C.; other modifications known or probable at other temperatures. In view of these statements and of the fact that phosphorus, arsenic and antimony are effective in increasing the resistance to dezincification, it was natural to assume that bismuth would act in the same manner. A series of tests was therefore carried out employing the methods described by Barry. Much to our surprise, bismuth did not inhibit dezincification, but rather seemed to accelerate it. Tensile-test speci-

Jan 1, 1942

By J. E. Burke, C. W. Mason

In attempting to study precipitation from a tetragonal lattice, using solid solutione of bismuth in tin, it was found that although a Widmanstätten pattern is observed1,4 only a qualitative analysis of the orientation relationships is possible, because of the unusual structural changes that accompany the precipitation process. Microscopical Studies Alloys were made from Chempur tin (Standard samples 42b and 426, National Bureau of Standards), and bismuth (Kahl-baum C.P.) by melting weighed quantities together under palm oil, stirring well, and castilig in a heated graphite mold. The polishing and etching techniques employed largely govern the visibility of the structural changes. The preliminary surfacing operations were similar to those recommended by Villela and Bergekoff,5 through Behr-Manning 3/0 abrasive papers, lubricated by a solution of paraffin in kerosene. A rough metallographic polish was next given, using a thin cotton cloth charged with relevigated alumina (maximum particle size of about 4µ) and soap solution; repeated etching and polishing served to remove disturbed metal. For high-power examination better preparation was necessary. It was found that on such soft metals the threads of the fabric, rather than the abrasive, cause most of the scratching. Cotton outing flannel, which had been brushed so that the nap lay down, was fairly satisfactory, but a heavy grade of silk velvet (not the noncrushable kind) was found to be better, especially after some use. A better procedure was as follows: The metal lap was warmed slightly, and a 4-in. circle of woolen broadcloth was cemented to its center by a thin film of melted paraffin. The broadcloth was then moistened with water, and a 30 to 40 per cent solution of sodium hydroxide heated to about 50°C. was poured over it, allowed to stand for I to 2 min. and then washed off. It was neither necessary nor desirable to remove all the sodium hydroxide from the cloth, since its etching action aided in the removal of the flowed layer from the sample. The cloth was then charged with a paste of the relevigated alumina in water. Since this lap did not remove deep scratches, it was necessary previously to polish the specimen on some material such as the silk velvet. The sodium hydroxide softens and partly gelatinizes the woolen lap covering, permitting a scratch-free polish, but its action continues, and the cloth deterioratcs after about 24 hr. This is not serious, because a new lap can be prepared in about 5 min., and only small pieces of cloth are used. Etching with a strongly acid solution of ferric chloride was found satisfactory for removing the flowed layer. For the final etching, the most satisfactory reagent was that of Tafls,7 the formula for which is: FeC13.6H2O, 2 grams; HC1, 5 c.c.; H2O, 30 c.c.; C2H5OH (95 per cent), 60 C.C. This etchant reveals differences in com-

Jan 1, 1942

By F. N. Rhines, A. H. Grobe

At elevated temperatures the oxide of silver is unstable in the air at atmospheric pressure, consequently no external oxide scale forms upon pure silver under conditions of high-temperature annealing. When small quantities of certain alloying elements are present in the silver, the formation of a thin external scale is possible1 and in addition there may form a subscale composed of the oxide of the solute element precipitated within the body of the silver. Norbury2 and Leroux and Raub3 have reported internal oxidation (subscaleiormation) in alloys of silver with 2, 7.5, and 30 per cent of copper. The presence of the subscale is believed to be responsible, at least in part, for the objectionable "fire mark" in Sterling silver.4 Several other alloys of silver, after oxidizing heat-treatments, are known to exhibit undesirable polishing characteristics that may be the result of internal oxidation. Except for the absence of an external scale of silver oxide, it is to be anticipated that silver alloys will prove to be very similar in their oxidation behavior to the alloys of copper, the oxidation characteristics of which have been studied in some detai1.5,6 The present research confirms this anticipation. The oxidation of a series of 20 dilute alloys of silver has been studied metallographically; some types of subscale not encountered among the copper alloys have been found. Instances of internal oxidation in alloys of most of the metals of the 1-6 and VIII groups of the periodic system are on record, but evidence of this type of oxidation in alloys of the metals of the intermediate groups is lacking. A number of the metals of the intermediate group, among them cadmium, lead, tin, and zinc, appear to provide the conditions essential to subscale formation; i.e., they form oxides with a relatively low negative free energy of formation, they dissolve other metals that form more stable oxides, and, presumably, oxygen will diffuse through them. In a study of 40 alloys of these white metals only a few cases of internal oxidation have been found. The probable reasons for this difference in behavior will be discussed presently. Experimental Procedure Silver.—The silver alloys employed in the oxidation studies were prepared in heats of 30 grams each from high-purity silver (99.993 per cent Ag)* and the purest avail-

Jan 1, 1942