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By Helmut Thielsch

During the last three decades a great many arguments have been presented on the subject of "mosaicJ' or "blockJJ structures of metals. Apparently because of insufficient evidence, the "block-structure" theories have never been widely understood among the physical metallurgists in this country, and most investigators among the few that have tried to demonstrate the existence of such an inner strutture Of crystals or grains have failed to recognize also the existence of a lamellar structure. Moreover, little thought has been given to justify the existence of such "lamellar" or "mosaic-block" structures on a theoretical basis. Since properties such as Plasticity; ferro-magnetism, hardness, diffusion, and others may be explained by structural faults in the lattice network of the crystals: the great importance of a more detailed knowledge of the structure within crystals or grains becomes now evident. Because Of the vast extent of the field Of submicroscopic structures, it shall be the purpose Of this paper only to review the more important of the results obtained by other investigators, especially in Germany, where a great deal of attention has been given to mosaic structure during the last three years. The origin of this mosaic patternt and effects of cold reduction and recrystallization will be shown in further studies later on. Imperfections in Crystals The many terms used in the literature to denote structural types of crystals are often not clearly defined. To clear up some of the confusion, the meaning of the more important terms will be given here. ideal, or perfect without any structural imperfections are called "ideal crystals,,or ''Perfect'' crystals,n meaning a Homogeneous interior structure of atoms, ions or molecules, as the case may be. In other words, at every point in the interior of the crystal exactly the same orientation of the crystallographic axes of the coordinate system would exist. The Surface of such a body, if etched with an appropriate etching reagent, would reflect light with perfect uniformity. Crystals of this type are almost nonexistent. Real Crystals.—L'Real crystals"' may contain various types of structural defects, which can be classified into: (I) lineage structure, (2) mosaic-block structure, (3) lamellar structure. The inhomogeneities many,in these groups mean that the orientation of the crystallographic aies will not be the same at every point within the interior of a crystal (or grain of a poly crystalline body). 'Perjecl Real Crystals.—The term "perfect real crystals " is generally used to describe crystals with minute structural or thermo-dynamical inhomogeneities. The former

Jan 1, 1946

By David R. Mitchell, E. A. Reilly, G. R. Gardner, F. P. Lasseter

THE methods that may be applied to the treatment of slurries and water, as these are related to practical coal-preparation problems, are concerned essentially with the movements of solids suspended in water. It is assumed that there are no fundamental differences between the principles involved in the treatment of coal slurries and the phenomena encountered in general mineral-dressing practice, and the latter are-presented in some detail. Basic principles are correlated with present practice for both the anthracite and the bituminous coal fields, and methods are discussed which are designed to utilize best all the material subjected to treatment and suggest a sound approach to the solution of problems relating to the return of clear water to process or to streams. In order to approach the practical phases of the subject with sufficient understanding of the basic principles, it is necessary to discuss two types of phenomena that are applicable. The first is flocculation and the second is sedimentation. Descriptive matter is given covering the various methods and types of equipment employed to conduct these operations, with emphasis on their application to water and coal-slurry treatment. DEFINITION OF TERMS Definitions of terms are consistent with modern developments, and conform, in general, with their usage in mineral-dressing practice. Because of variations in coal-preparation methods, it is impossible to define a rigid upper limit of particle size for a coal slurry or sludge which will apply generally. Limits vary somewhat with the particular treatment method employed at a given plant. For purposes of definition, this limit is chosen as the particle size for which preparation methods such as Chance comes and jigs are usually dispensed with, and other methods, such as the Hydro-tator, tables, and froth flotation, are employed. Generally the limit will be 10 to 6 mesh.

Jan 1, 1950

By George H. Found

During recent years considerable interest has been focused on the energy-absorption characteristics of metal when it is cyclically stressed in vibration. The most familiar manifestation of this phenomenon, which is called the "damping capacity" or "internal friction" 06 a material, is involved in the dissipation of mechanical energy of vibration, which otherwise would build up to stress levels where the problems of noise and fatigue are involved. In addition to its engineering importance in structures, the damping behavior of metals, particularly at low stress amplitudes, has also been used as a unique metallurgical research tool with which to provide sensitive means for indicating certain structural changes within metals. Important contributions toward understanding the energy-dissipating -mecha-nisms that are responsible for internal friction in metals have been made in the last few years. The information is not yet sufficiently extensive, however, to provide a useful metallurgical concept describing exactly how the structure affects the internal friction, or to encourage more general use of this technique among metallurgists. Three fundamental mechanisms have been proposed, as a result of recent experi- mental investigations, to account for the internal friction in nonferrous metals in low-stress amplitude tests. These include damping due to internal thermal currents that are created and flow in metal because of differential vibratory stress effects,' damping due to localized inelastic stress relaxation at inhomogeneities within the meta1,2,3 and damping related to plastic flow of a localized type for which an explanation has been sought in terms of the dislocation theory.' How each of these mechanisms functions as a result of structural changes in the metal is, in general, not well understood because of insufficient experimental data for which the controlling variables ham been segregated and because of uncertainties in regard to the nature of the structural changes themselves. In several investigations the effects of cold-working on the internal friction of polycrystalline brass and aluminum have been described. As reported by Köster and Rosenthal,5 and by Förster and Breitfield,6 there is an initial large increase in the damping when the metal is worked. The initial high value is not stable, but declines rapidly, at first, in a hyperbolic manner. About Ioo hr. after straining, a stable value is reached of magnitude proportional to the amount of strain.' In Fig. I is shown the relationship found by Zener and his collaborators between the internal friction due to cold-working of alpha brass and the amount of cold-working.8 Several investigators have made internal-friction measurements on worked poly-

Jan 1, 1945

By N. A. Stockett

SOUTHEAST Missouri is the largest and oldest lead-producing district in the United States. For the year 1941, the statistical picture of pig-lead production, stated in short tons (partly estimated by the Engineering and Mining Journal) is as follows. [Tons World production 2,000,000 United States production 460.000 Southeast Missouri production 242,000] The consumption of primary lead in the United States in 1941 was approximately 900,000 tons, or almost double the country's production. The largest previous year's consumption in the United States was 718,000 tons, in 1926. The largest quantities of lead are used for cable sheathing, storage batteries and white lead. During 1941 tetraethyl lead for auto and aviation gasoline consumed 50,000 tons of lead. The entire lead production of Southeast Missouri is now mined by the St. Joseph Lead Co., whose dominant position as the largest producer in the United States of lead directly from ores is best shown by the fact that in 1941 it produced approximately 31 per cent of the lead production of the United States from its mines in southeast Missouri, where 22,000 tons of ore, averag¬ing over 3.00 per cent lead, is mined per working day. It is known that lead was mined at Mine La Motte, Madison County, Missouri, by Renault in 1723. Other white men and Indians probably did some mining prior to that time. Since 1865, the recorded production to Jan. 1, 1942, shows that the St. Joseph Lead Co. and the various other companies that have operated in St. Francois County mined lead ore, which, after milling and smelting losses produced 5,00,000 short tons of pig lead. About 95 per cent of the present lead production of Southeast Missouri is mined in St. Francois County. The northern part of this area is 60 miles south of St. Louis. The remainder of the lead is obtained at Mine La Motte, about 25 miles southeast from the center of the producing area in St. Francois County. PROSPECTING In this district, most of the ore is discovered by surface and underground diamond drills and by prospect drilling underground with rock drills. Each 2-ft. length of the cuttings from these Jackhamer prospect holes is assayed for lead. These holes are marked and the records are entered on maps. It has been found that close drilling--100-ft. centers of holes, and sometimes less-is necessary in order to locate most of the smaller commercial ore bodies, many of which previously had been missed by drilling the areas with holes spaced 200-ft. centers or more.

Jan 1, 1943

By G. Howell Clevenger

FORMERLY great divergence of opinion existed in regard to the influence of copper in steel, as affecting its various physical properties. More recently the investigations of Stead,1 Breuil,2 Wigham,3 Burgess and Aston,4 Ball and Wingham,5 Miiller,6 Dillner,7 and others have shown fairly good agreement in the major points. Copper steel has been shown by these investigators to possess special properties which make it valuable for certain uses. The general range of composition of the useful alloys of copper and iron, and of copper, iron, and carbon, has been quite definitely established, for the former by Burgess and Aston,8 and for the latter by Breuil 9 and Stead.10 Stead 11 has removed one difficulty in reconciling certain of the earlier data by calling particular attention to the influence of carbon in copper steels. Another point which caused confusion in the earlier investigations, particularly in regard to " red-shortness," was the presence of sulphur. Failure to note the presence of sulphur often led to attributing " red-shortness " to the presence of small amounts of copper. Turner 12 has called attention to the fact that where copper exists in an iron ore it often occurs as the sulphide, so that the presence of copper in steel made from such ores might also, necessarily, mean the presence of sulphur. It is evident that the effect in this case might be quite different than where pure copper was added.

Jan 10, 1913

By Elbert Rowland

THE widespread interest in the alloys of beryllium with copper is due principally to the fact that certain compositions show very favorable precipitation-hardening characteristics and are, in fact, the strongest nonferrous alloys known at the present time. Investigations have been conducted by Masing and Dahl and others on the physical characteristics of ternary beryllium alloys, in an attempt to produce precipitation-hardening effects with a smaller amount of beryllium than that required in the binary copper-beryllium alloys (2.0 to 2.5 per cent Be). The results of these investigations show that ternary alloys of beryllium with Cu-Sn, Cu-Al and Cu-Zn, among others, exhibit promising improvements in physical properties after precipitation-hardening treatment and, while the increases in properties obtained are not as high as those realized from the binary copper-beryllium alloys, excellent properties are obtained with beryllium contents averaging about one-half the amount required in the binary alloys. This paper presents the results of an investigation of the equilibrium relations of certain alloys containing copper, tin and beryllium. The alpha-phase boundary of the ternary system is given for alloys containing from 0 to 1 per cent beryllium. The equilibrium conditions beyond the alpha-phase boundary are presented for alloys containing up to 32 per cent tin and 1 per cent beryllium. The data were collected by means of

Jan 1, 1935

Many definitions have been advanced and many limitations advocated in the use of the terms, veins, lodes and ledges. The following definitions appear to follow the best usage. [ ] A fissure vein, according to Lindgren, is a mineral mass tabular in form as a whole, though often irregular in detail, filling or accompanying a fracture or series of closely set and intimately related parallel fractures in the enclosing rock, the mineral mass having been formed later than both the country rock and the

Jan 1, 1932

By Frank F. Aplan

In looking into the crystal-ball scene of minerals beneficiation for 1970 and beyond, an impartial observer becomes con- fused as to what has been done and what is possible in the way of improvements. The mining official must balance the burden which is being shouldered by the mineral industry for maintaining our environment in its pristine state on one hand, with the solid advancements made in technology and cost savings on the other hand. Then the official wonders if this is really the criterion for judging overall performance today. As a prospective engineer, Dave Bolles sees it this way: "Specialization has caused many engineers to subordinate everything to doing their job the cheapest and fastest way. In the future this won't be enough. The engineer in the mineral industry will be responsible not only for mining, concentrating and smelting, but also for the resultant wastes- the mine dumps, the tailing dams and the slag piles." (See Drift on page 63).

Jan 1, 1971

By Frank J. Tolonen, Nicholas H. Manderfield, Paul Jasberg

EARLY in the study of the low grade iron formations of Michigan, wide variations in their structure and texture became evident. Because of these variations no simple method of concentration is possible, and those portions of the formations that can be exploited profitably under a given stage of metallurgical progress and existing economic conditions must be searched for carefully. Both structure and texture of the formations have an important bearing on their amenability to beneficiation. By structure is meant the banding planes of easy fracture, the porosity, and the degree of leaching. Texture, which includes grain sizes, shapes, and degree of interlocking, determines the amount of grinding necessary to liberate the mineral grains. Structure determines the liberation of portions richer in one mineral. Structure and texture may be termed the gross features of the formation

Jan 11, 1957

By C. A. Zapffe

BOTH the foundryman and the theoretical metallurgist are now generally agreed that the anomalous "rising" or "bleeding" of certain ferrous castings of killed metal is primarily attributable to hydrogen. How and why the phenomenon occurs, however, have not been made clear. The following discussion is intended to harmonize foundry experience with metallurgical theory so that the foundryman may possibly improve his ability to prognosticate whether a certain casting may bleed or not. BLEEDING, RISING, AND PIPING The "rising" to be discussed here is not to be confused with the action in rimming ingots as a result of the carbon-oxygen reaction, although a conclusion will be drawn that may apply to the art of controlling the rimming action. Only killed metal is considered, which includes both steels and irons. In Fig. I, three killed, chill-cast ingots are shown: a porous ingot whose evolution of gas during late stages of solidification has ejected metal through the top; an ingot in which moderate gas evolution during solidification has lifted the mushy central metal, i.e., it has "risen"; and, third, a sound ingot with good piping characteristics. The first type is referred to as "bleeding," and generally infers that a solid skin had first formed through which the liquid metal later erupted. There is no fundamental distinction between bleeding and rising in reference to killed metal.* POROSITY Hydrogen appears as a cause of bleeding because the gas evolution simultaneously leaves a porosity of a type traceable to hydrogen. Twenty years ago, Melmoth1 noted that killed steel that rose unexpectedly in the mold, if returned while liquid to the furnace and heated further under a reducing lime slag, would again rise in the mold; but that if the ingot were allowed to solidify and was then remelted no rising occurred. A critical quantity of the responsible gas is therefore removed by the rising action. Melmoth associated rising with high silicon (0.7 to 0.9 per cent) and concluded that silicon increased gas absorption. Because silicon is a strong deoxidizer, oxygen must, therefore, be eliminated from consideration of the three common gases in steel-oxygen, nitrogen, and hydrogen. Butterworth2 later decided that pinhole porosity was caused by gases dissolved in the metal and that hydrogen was obtained from steam in the mold. Allen's classical work on copper castings,3 soon followed by

Jan 1, 1942

By W. H. Brandt

THERE has been much progress in the last two decades in understanding the hardenability of steel. Roughly, the progress has been along two lines, which may be designated as empirical and fundamental. This empirical work has progressed to the point where steels may be manufactured to the desired characteristics quite closely and heat-treatment and application problems can be approached with considerable confidence. Particularly noteworthy among the empirical work is that of Grossmann,12 who has given formulas for calculating hardenability as a function of composition, and the establishment of the isothermal transformation curve by Davenport and Bain.13 The latter does not fall entirely in the class of an empirical study, for while it provides a means of presenting a tremendous amount of empirical data in the form of a single curve, it also outlines clearly the problems that face the fundamental investigator. The isothermal transformation curve shows clearly that the phenomena occurring in the neighborhood of the knee of the curve are those that limit the hardenability of steel. Above the knee of the curve, the product of decomposition of austenite is lamellar pearlite and fundamental progress has consisted chiefly of a detailed study of structure and formation of pearlite, largely at the hands of Mehl and his collaborators.1-5 They have shown that formation of pearlite proceeds by a process of nucleation and growth and they measured both the nucleation and growth rate. However, there is still a wide gap between our empirical knowledge and fundamental knowledge, owing largely to the fact that there is no satisfactory theory of nucleation rate or of growth rate. This paper is being written in an attempt to fill in a small part of the gap. A method was presented recently14 for calculating the velocity of edgewise growth of pearlite using an expression for the carbon concentration that satisfies the diffusion equation. The edgewise velocity of pearlite growth in a plain carbon eutectoid steel was calculated, using linear extrapolations of the ferrite and cementite solubilities. While the results are in fairly good agreement with the experimental facts, the calculated velocity of edgewise growth is smaller at 600°C. than G, the radial growth velocity of pearlite nodules, whereas one would expect it to be larger. In this paper the calculation will be repeated using a new extrapolation for the ferrite solubility, which gives better agreement between G and V, the calculated velocity of edgewise growth. A calculation will also be made of the effect of carbon content on velocity of edgewise growth, and the problems of calculating the effects of other alloying elements on growth rates will be discussed. It will be assumed that the mechanism of pearlite growth, established by Mehl and

Jan 1, 1945

By R. T. Walker

GROUND waters-hot or cold-containing small amounts of the more common earth acids, such as carbonic acid, silicic acid, hydrogen sulfide, sulfurous acid and sulfuric acid, have only a very limited "solvent effect on dominantly siliceous rocks, whether of igneous or sedimentary origin, but in limestone they often form extensive cavities; and such "limestone caves" are the only openings of considerable size and continuity in rock formations that do not owe their existence directly and almost wholly to dynamic action. Limestone caves such as are developing at the present time must have been formed in all past geological ages in which limestone beds existed and where suitable conditions for the development of such caves prevailed; hence it would seem a reasonable expectation that, in the course of geological history, a certain number of ancient limestone caves must have been utilized as channels for the passage of mineralizing solutions, during portions of their course, at least, and that, in consequence, orebodies must have been deposited in such caves. Such a conception is not novel; it was proposed many years ago, but its possibilities, as explaining certain types of ore deposits, have been rather lost sight of in the development of the theory of the metasomatic replacement of rocks by minerals. It is the purpose of this article to assemble evidence to show that many of the orebodies found in limestone beds have been deposited in pre-existing caves; to discuss the criteria whereby such orebodies can be distinguished from others which have been formed along fissures and fracture zones traversing limestone, by the more common method of metasomatic replacement, analogous to orebodies in other formations; and to describe certain orebodies-particularly the "ore channels" of the Tintic district, Utah-as illustrative of the principles discussed. Limestone caves may be divided into two classes: those formed by cold, descending surface waters, which emerge again at some lower elevation as cold springs; and those formed by hot, ascending waters of deep origin or circulation, which attain the surface as thermal springs. Although these two classes are similar in many respects, there are certain characteristic and inherent differences whereby they can usually be distinguished.

Jan 1, 1928

By Daniel Hanson

FoR most of their practical applications metals are required to withstand stresses of appreciable magnitude: indeed, it id because they possess the quality of resisting stress without becoming permanently deformed that they find such extensive use in the service of man. Metals and alloys must, in service, usually behave as elastic substances—or nearly so. It is not difficult to satisfy this condition at ordinary temperatures. Iron and its alloys, especially the steels, are at normal temperatures excellent elastic bodies, capable of satisfying most of the mechanical requirements of the engineer: where electrical, chemical or other properties are impor-tant, which cannot be met by steels, it is usually possible to find a non-ferrous alloy such as nickel, copper or aluminum, which will prove satisfactory. When the metals or alloys are not inherently sufficiently elastic, cold-working or heat-treatment may develop elastic properties to a sufficient extent for practical needs. By means of relatively simple, rapid tests we can measure such properties as elastic modulus, limit of proportionality and proof stress, upon which design can be based with confidence. The case of the soft metals, such as lead and tin, is well known to be exceptional. They possess no definite limit of elasticity, and the value of proof stress or tensile strength depends to a great extent on the speed with which the test is carried out. Design here must be based on other considerations than a well-established theory of the proportionality of stress and strain. It is now generally recognized that steels and non-ferrous alloys possess at temperatures not greatly exceeding that of the atmosphere, characteristics quite different from those existing at ordinary temperatures, and that they assume qualities similar to those of the soft metals. Not only have they no limit of elasticity, but the proof stress and the ultimate stress depend on the time of application of the load. Flow under load may persist for long periods of time, possibly indefinitely, and the determination of a true maximum stress becomes a matter of great difficulty.

Jan 1, 1939

By Daniel Hanson

FoR most of their practical applications metals are required to withstand stresses of appreciable magnitude: indeed, it id because they possess the quality of resisting stress without becoming permanently deformed that they find such extensive use in the service of man. Metals and alloys must, in service, usually behave as elastic substances—or nearly so. It is not difficult to satisfy this condition at ordinary temperatures. Iron and its alloys, especially the steels, are at normal temperatures excellent elastic bodies, capable of satisfying most of the mechanical requirements of the engineer: where electrical, chemical or other properties are impor-tant, which cannot be met by steels, it is usually possible to find a non-ferrous alloy such as nickel, copper or aluminum, which will prove satisfactory. When the metals or alloys are not inherently sufficiently elastic, cold-working or heat-treatment may develop elastic properties to a sufficient extent for practical needs. By means of relatively simple, rapid tests we can measure such properties as elastic modulus, limit of proportionality and proof stress, upon which design can be based with confidence. The case of the soft metals, such as lead and tin, is well known to be exceptional. They possess no definite limit of elasticity, and the value of proof stress or tensile strength depends to a great extent on the speed with which the test is carried out. Design here must be based on other considerations than a well-established theory of the proportionality of stress and strain. It is now generally recognized that steels and non-ferrous alloys possess at temperatures not greatly exceeding that of the atmosphere, characteristics quite different from those existing at ordinary temperatures, and that they assume qualities similar to those of the soft metals. Not only have they no limit of elasticity, but the proof stress and the ultimate stress depend on the time of application of the load. Flow under load may persist for long periods of time, possibly indefinitely, and the determination of a true maximum stress becomes a matter of great difficulty.

Jan 1, 1939

By F. L. Wolf

THE catenary system of line construction possesses so many desirable characteristics from the operating standpoint that it has wide application for all types of electric traction. Many steam roads are electrifying sections of their lines, and in most cases are operating both steam and electric locomotives over the same track. This' means that the overhead catenary system is subjected to the severe corrosive action of locomotive smoke, and data concerning the resistance of various alloys to this form of corrosion are very desirable from every point of view. Reliable and specific information and data on the subject of corrosion due to steam and smoke from locomotives are extremely meager and, on this account, extensive service tests, together with accelerated tests, have been made on a number of commercial metals and alloys. The observations and data recorded in this paper are the result of a, preliminary test which was started in 1923 and which has been carried on to the present time. The recognition of the need for even more detailed and accurate data has resulted in the undertaking of another test which has been in progress for about a year. The result of this test will be published in due course. Some years ago The Ohio Brass Co. was asked by one of the large steam railroad companies to furnish data on construction details for a catenary system which it was considering for one of its divisions. The selection of, materials which would give the necessary physical characteristics as well as withstand the severe corrosive action of locomotive gases caused electrical railroad engineers considerable concern. At that time, there were available no specific or authentic data on these important questions: no systematic investigation of the problem appeared to have been made, even though its importance was generally recognized. Such observations as had been made were crude in that they had been limited largely to visual inspection which too frequently is most misleading. However, the scattered information which was collected gave important clues as to how best to start an investigation.

Jan 1, 1930

By Fritz F. Prugger, Peter R. Jones

This paper considers some of the main aspects of underground mining in the flat, rich, but deep lying deposits of Saskatchewan. It briefly describes the pertinent geological features as they relate to mining and the practical de-stressing techniques used to allow productive extraction in the high stress environment present in many of the province’s mines. Mining layouts, materials handling, and the evolution of some of the world's largest mining equipment are examined.

Jan 1, 1983

By D. J. MacKinnon, J. M. Brannen

Smooth, compact, dendrite free 24-h zinc deposits have been electrowon from zinc chloride electrolyte using a diaphragm cell. The cell consisted of sealed anode compartments containing DSA anodes separated from an open cathode compartment by Dynel cloth membranes. Fresh electrolyte was fed to the cathode compartment where zinc deposition onto an aluminum cathode was aided by air sparging. The catholyte passed through the diaphragms into the anode compartments from which chlorine gas and spent anolyte were withdrawn. Standard electrolysis conditions were: 15 g/L Zn, 0.12 M HCI, I5 mg/L tetrabutylammonium chloride (TBACI) as the addition agent, 35°C, and 323 A/m2 (30 ASF) current density. The effect of variations in these conditions on the morpohology orientation, current efficiency, and energy requirement for 24-h zinc deposits was determined. The effect of total chloride ion concentration on the zinc deposit was studied by adding various amounts of NaCl to the electrolyte.

Jan 1, 1983

By C. S. Simons

Manufacturers of filtering, thickening or clarifying equipment, have been active in developing machines to meet increasingly rigid operator requirements, and the innovations resulting from this effort are moving into commercial applications. In general, the results of these applications are reported to be good. Little has been reported on progress in theory. The growing insistence on the part of pollution control agencies that waste water discharged into streams contain less and less suspended solids is being felt by a broad cross section of industry. A new clarifier, based on the often rediscovered fact that suspended solids settle more rapidly in inclined channels, is being marketed by Neptune MicroFLOC of Corvallis, Ore. This unit employs modules of inclined tubes, mounted in the upper zone of the clarifier, which carry the water flow. These were developed for light solids, such as those encountered in domestic water treatment and in paper mill waste water. In these applications, flow rates up to about three times those permissible in conventional clarifiers are reported to give comparable overflow turbidity. By combining these units with mixed media filters, high clarity may be obtained with minimum capital. Use of such units in the metallurgical industry, particularly where water reuse or effluent quality is important, should grow.

Jan 1, 1970

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

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

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