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By J. G. Morlet, A. R. Troiano, H. H. Johnson

Delayed failure in steel occurs by controlled initiation and growth of a crack. The incubation period for crack initiation was measured. Crack initiation and Propagation are controlled by interaction between hydrogen concentration and triaxial stress state. The incubation period results from stress-induced diffusion of hydrogen to the point of crack initiation. THIS paper describes the phenomenon of delayed failureland the kinetics of crack initiation and propagation in uniformly hydrogenated steel. The investigation was prompted by service failures of high-strength-steel components at applied stresses far below the conventional yield strength, after the part had successfully sustained equal or higher stresses for an extended time interval. This delayed failure phenomenon, often termed static fatigue, is associated1 with the presence of hydrogen. This is not surprising, since the voluminous literature on flaking and hydrogen embrit-tlement demonstrates that hydrogen may exert a potent embrittling influence. Flakes, or internal hairline cracks in alloy-steel forgings, are related to the presence of hydrogen retained from the steel-making process.2 On the other hand, embrit-tlement arises from hydrogen introduced during surface treatments such as acid pickling or electroplating. Laboratory delayed failures have been induced in notch specimens of 4340 steel by electrolytic charging of the specimen surface with hydrogen and subsequent static stressing.l,4,5 Static fatigue was observed over a wide range of applied stresses; however, failure did not occur below a critical applied stress, designated as the static fatigue limit. In this instance the extended time for failure resulted primarily from the macroscopic redistribution of hydrogen. A crack formed to the depth of the hydrogen enriched "case* upon loading; further crack growth naturally awaited diffusion of hydrogen into the material ahead of the crack. The crack-propagation rate was therefore controlled primarily by the macroscopic diffusion of hydrogen into the specimen interior during the test. Thus, in this instance static fatigue was associated with the movement of a gross concentration gradient. However, delayed failure in steel of uniform hydrogen concentration is of greater fundamental interest, as well as commercial significance. With a homogeneous hydrogen distribution a different mode of delayed failure might be expected. As the heterogeneous hydrogen distribution became more uniform,4,5 the initial crack-propagation rate decreased markedly and, in fact, what appeared to be an incubation period for crack initiation was observed. However, the macroscopic concentration gradient precluded an accurate evaluation of these observations. Although the existence of an incubation period, up to this time, has not been established definitely, it is not amiss to point out some implications of the concept. It is of interest in all hydrogen-induced embrittlement phenomena, such as flaking, delayed failure, and hydrogen embrittlement. Much discussion has centered around the possibility of an

Jan 1, 1959

By Morris Cohen

IT has been known for several years that in certain age-hardenable alloys precipitation of finely divided particles occurs simultaneously with the changes in physical properties; while, in other alloys, these changes take place prior to, or without any, precipitation. . The silver-copper alloys are generally considered to be the classical example of the first group, and the aluminum-copper alloys (duralumin) are typical of the second group. The two types of aging are explained by the precipitation theory and the knot theory respectively. ? It is well recognized now that these theories do not conflict with each other; the one used for a given aging system depends upon which way the alloy in question happens to age-harden. However, previous work on the aluminum-copper alloys1,2 has shown that if the aging temperature is raised sufficiently the hardening will be accompanied by actual precipitation. In fact, it is quite probable that all of the so-called knot-hardening alloys will harden by precipitation at elevated temperatures. Therefore, a combination of the knot and precip-itation theories is necessary to give a complete picture of the age-harden-ing of these alloys, and indicates that knot formation and precipitation are not independent processes. To test the generality of this concept, it is necessary to show that the alloys that commonly harden by precipitation will harden prior to precip¬itation if the aging temperature is sufficiently lowered. For this reason, it would be well to carefully re-examine the aging characteristics of the silver-copper alloys at aging temperatures somewhat below those used by previous investigators. If hardening can be detected prior to precipi¬tation in these alloys, it will lend great weight to the idea that knot forma-

Jan 1, 1936

INCREASING realization that pouring and ingot-mold practices involve many factors of fundamental importance to ingot quality and general steel-mill operations has caused these phases of steelmaking to become major concerns of operators and metallurgists engaged in control of quality and costs. Methods of pouring steel from the ladle into the ingot molds have some direct effects on ingot quality. The mold itself governs solidification and dimensions of the ingot and in so doing exerts some very tangible influences not only on ingot quality but also on product yields and general steel-mill processing. In addition, practices are employed in the handling of molds during daily open-hearth operations that are important to quality and production costs. Therefore, pouring and mold practices must be considered highly specialized and important steps in steel-mill operations. MOLD DESIGN Mold design is difficult to discuss in a precise manner because it varies greatly throughout the industry, both in theoretical concepts and practical application, and few well developed data are available. Most ingot molds are designed to meet conditions peculiar to a given plant wherein quality standards are dictated by end-use requirements, which may differ considerably even for the same grade of steel. The mold designer must also consider the equipment available to process ingots and the product obtained from them. Such equipment, used for stripping, heating, blooming and finishing operations, is seldom, if ever, exactly the same in any two steel plants. Thus, pronounced contrasts in mold designs can be expected to continue, even among plants making strictly comparable types of product, particularly because some producers are just beginning to realize the benefits possible from specialized designs. Certain fundamentals are used in mold design but even these

Jan 1, 1964

By C. H. Brehaut, W. N. Taylor, R. S. Douglas, H. A. Shannon

THE name for this new method of mining is derived from a composition of Horizontal, Radial, Diamond, and the drilling is from raises. This method, worked out at Copper Mountain, B.C., is believed to be distinct in many features from other known methods. GEOLOGY The ore deposits of Copper Mountain are related to the Copper Mountain stock, which is an ideal example of the magmatic differentiation in that it grades from a basic gabbro at the border to an almost pure orthoclase-pegmatite core. The "contact" ore bodies lie along the contact of the gabbro and an older complex of volcanics and sediment termed the "Wolfe Creek" formation. These older rocks, collectively referred to as greenstone, had been fractured prior to the intrusion of the stock and were highly metamorphosed during the intrusion. The "outlying" ore bodies are somewhat different in character, though a similar structural pattern prevails. It is believed that a deep-seated magma of which the Copper Mountain stock is a part has given off solutions that caused a partial granitization of some of the volcanics. Mining problems are caused further by the presence of a series of soft barren dikes intersecting a great many of the ore bodies, which are about 30 ft. wide, strike north-south, and dip at a high angle to the east; and are further increased by the presence of four major faults, with a great many minor faults running at acute angles from them. Fault zones average 8 ft. in width, and consist of gouge and breccia. They strike northeast and dip steeply to the northwest. The faults cut through the ore zones and the dikes, and continue on into the gabbro. The general mine structure with two types of ore bodies, bounded by weak walls and intersected by several series of soft barren dikes and major faults, indicated that a method of mining should be devised that would remove the ore at low cost with the least disturbance of the waste walls and dikes. THEORETICAL ESTIMATE OF STOPING WITH THE DIAMOND DRILL After consideration of various methods, the most suitable one appeared to be horizontal drilling to break the ore in a manner similar to shrinkage stoping. Drilling vertical holes or rings from a bench and breaking to an open slot was eliminated because the weak walls of ore, dike or waste would not permit this type of opening. It was then decided to drill either horizontal radial holes from a raise or parallel holes from a slot cut across the ore body. After discussion, the latter method was believed unsuitable, for the following reasons:

Jan 1, 1945

By T. W. Bossert

MELTING is the initial step in the fabricating of all aluminum and aluminum-alloy products. Its function may be considered as threefold: to improve the metal quality, to adjust the composition, and to change the form to that required for subsequent fabrication. Because the melting operation is generally somewhat removed from the final product fabrication, its importance is frequently overlooked. Melting equipment and melting procedures can reflect materially on fabricating procedures as well as on quality and cost of final product. The selection of equipment and the establishment and control of melting procedures, therefore, should be given careful consideration. It is the purpose of this paper to present the various factors that should be considered in establishing melting procedures and in selecting melting equipment. Certain of these are the result of the inherent characteristics of aluminum and can be treated rather specifically. Others depend on the particular production requirements and hence will have to be considered more generally. This paper is intended to cover only the melting of solids, as differentiated from fines, such as borings, turnings, and sawdust. The melting of fines, in many respects, is a subject that should be treated by itself, and practices for melting fines are by no means as standardized as are those for melting solids. The melting of fines is today the subject of considerable developmental interest; hence practices discussed today may soon be replaced by new or improved ones. CHARACTERISTICS OF THE METAL THAT AFFECT MELTING Aluminum and aluminum alloys possess several inherent characteristics that affect the melting problem. Of the physical properties, density, heat content, thermal conductivity, emissivity, and melting temperatures are important because of their effect on equipment design. A list of such properties for commercially pure aluminum is given in Table r, compared with similar properties for iron and copper. The low density of aluminum as well as of the aluminum alloys is of material advantage in the design of melting equipment, in that such equipment can be considerably lighter than similar equipment for handling the heavier metals. The density, however, particularly of the molten metal, is not greatly different from that of the oxides and other nonmetallic materials that develop or become part of the melt during the melting process. Separation of such nonmetallics is not as rapid a process as with some of the other metals, and consideration of this must be made in establishing melting procedures. Sufficient holding time to permit such materials to separate out and, in some cases, fluxing treatments to aid the separation, are required. Since some of these nonmetallics settle to the bottom of the melt, provision should also be

Jan 1, 1946

Thomas Haight Leggett, London, Eng. (communication to the Secretary): Mr. Hammond has given us a concise yet complete description of the Witwatersrand gold-fields, and the character of the operations which have resulted in their remarkable development.

Jan 1, 1902

By G. Pizzi, G. M. Ciucci, G. L. Chierici

The use of the material balance equation to estimate the volume of hydrocarbons originally present in a reservoir, whose producing mechanism is partly due to water drive, has been discussed in the literature by several authors. There is no general agreement upon the possibility of obtaining reliable results by this method. Gas reservoirs in contact with an active aquifer are considered in this paper. Theoretical considerations based on the cybernetic principle of uncertainty (which states that the internal structure of a system cannot be uniquely determined from its observed external behavior) lead to the conclusion that the volume of gas originally present in a reservoir of this type cannot be uniquely determined from its past history. The range of values which encompasses the actual value of the reserves varies from case to case and must be determined by either numerical or analogical methods. Results obtained for six gas fields are reported. All these fields were produced with small fluctuations in their production rates, as is common practice for gas reservoirs; no gas storage fields were considered. Results obtained show that reserves values in a range of 1 to 2, associated with appropriate aquifers, allow the matching of the reservoir past history with mean-square deviations less than the experimental errors involved in pressure and produclion measurements. Similar results have been found in several other partial water drive gas reservoirs. From these results it is concluded that gas reserves cannot be uniquely determined from the past performance of partial water drive reservoirs, at least in cases where the reservoir has been submitted to small fluctuations in the production rates, and pressure data of normal accuracy are available. INTRODUCTION A number of authors have analyzed the problem of estimating the reserves originally present in a partial water drive reservoir from its past pressure-production performance. Literature which deals with this subject can be grouped, according to their conclusions, as follows. 1. A reliable value for the reserves can be obtained even if reservoir data (pressure and cumulative production) are affected by errors within the normal range.'-' 2. A reliable value for the reserves can be obtained only if reservoir data are very accurate'- or if past production performance has been subjected to abrupt variations in the production rate."' 3. No unique value for the reserves can be obtained from reservoir past production performance. This conclusion has been based upon theoretical considerations" and verified in several field cases. The purpose of this paper, which deals only with partial water drive gas reservoirs, is to test the above conclusions against actual field cases. Some theoretical considerations on this problem are also presented. THEORETICAL CONSIDERATIONS As the behavior of a gas reservoir communicating with an aquifer depends on both the aquifer and the reservoir characteristics, the physical system to be studied is the combined gas reservoir plus aquifer. The information which is available for studying the performance of such a system is the well production rates and bottom-hole pressures, all given as functions of time. The external behavior of the reservoir-aquifer system is therefore described by 2n input variables (Gp, Wp,) and n output variables (p,), n being the number of wells in the reservoir. In reservoir engineering it is common practice to consider the reservoir as a whole, disregarding the internal distribution of pressures and of producing wells. This practice is equivalent to substituting the above multi-variable system with a single-variable system, where the average reservoir pressure is the only output variable and the cumulative production G,(t) and W,(t) are the input variables. The internal structure of such a system, defined by initial gas reserves G, aquifer shape and dimensions, boundary conditions and petrophysical parameters distribution throughout the aquifer, is unknown. Therefore, from a cybernetic point of view the system is a "black-box It has been demonstrated" that for a blackbox the indetermination principle holds. Accordingly, the number of different internal structures (or set of parameters) which can account for the observed external behavior is infinite. As a consequence, the initial reserves cannot be uniquely determined from the reservoir past performance. When W,(t) is known, the determination of G from

By William B. Plank

AGAIN the records show an unprecedented enrollment of students in the mineral technology schools of the United States and Canada. In the current year, 1938-'39, 9619 students were resident in the 53 schools of the United States arid 1014 in the six schools of Canada. These data are from my fifth study of the mineral technology schools of the United States and Canada. the last previous study having been made for the year 1936-'37. The undertaking as previously was made under the auspices of the Mineral Industry Education Division of the A. I. M. E. The data or, the various schools were collected in the same way as for former studies.

Jan 1, 1939

Discussion, at the Virginia Beach Meeting, February, 1894, of the Paper of Prof. Posepny. (Trans., xxiii., 197, 587.) Including communications subsequently received. a T. A. Rickard, Denver, Colorado (communication to the Secretary) : The paper of Professor Posepny was printed so short a time

Jan 1, 1895

By Frances Hurd

WHEN 60:40 brass is heated to 825° C., given a drastic quench to obtain the beta solid solution, and reheated, various changes take place in the structure. Reheating at 200' C. causes a fine, granular, sorbitic structure to appear which has been considered alpha solid solution. These particles coalesce at higher temperatures of reheating, and at 470° C., the alpha forms twins. A further study of these transformations was considered worth investigating.

Jan 1, 1927

By Arnold K. Reese

It is not the purpose of the writer to set forth in these notes anything new or surprising in blast-furnace practice, but simply to lay before the Institute the somewhat unusual results obtained during a period of six consecutive months, ending April 30, 1896, at the Dover furnace of the Penn Iron and Coal Co., and to give, with these results, the conditions under which they were obtained, and all figures pertaining to that period. This plant was entirely rebuilt, on thoroughly modern and improved plans, in the spring of 1895, by Frank C. Roberts & Co., of Philadelphia.

Jan 1, 1898

By S. H. Ash, J. J. Forbes

Probably the newest thing in mining safety, or safety for mines, is the apparent dissatisfaction on the part of the mineral industries, as represented by both management and labor, and the general public of the Nation, with the safety record of the mining industry. This is reflected by published comments and papers in the technical press;l-9 in labor periodicals,10,11 in popular journals and periodicals,l2, 13 and in the daily press; also by discussions of the Safety Committees sponsored by the National Safety Council,9, 14-15 the American Mining Congress,l.l6 the American Institute of Mining and Metallurgical Engineers,2,4 the Mine Inspectors' Institute of Amerthe Coal Mining Institute of America,5 19 the American Standards Association, and others.20.21 Mining safety is a joint problem of management and the individual workman. Safety is not attained and will not be attained solely by laws, decrees, and commands because, if it could be done in this manner, acceptable mining safety would have been achieved long ago by the individual states in our Nation and by the nations abroad. The best safety performance is found at plants where management provides a safe environment for the workers; where supervision is efficient and super- visors, others concerned with promoting safety, and the individual worker know through training, experience, and personal contact the safe and unsafe practices of their field; and where the trained individual worker has become safety-minded by experience, quiet influence, unconscious suggestion, and personal guidance. Despite what may be said to the contrary, progress has been and is being made in mining safety. This is shown in Fig 1 to 4. It is beyond the scope of this paper to give possible reasons for the valleys and peaks in the fatal-injury rates. Some recent factors that appear to be contributing to the improvement in these rates are briefly discussed. Aside from mining equipment, "what's new in mining safety" for some mines has been in effect or was tried by others long ago. A safety pro- gram is a living thing; as such, it must be vitalized and continuously fed with enthusiasm, constructive action, and improvements. Because safety is concerned with human conduct, it is necessary to practice safety at all times; if not, it is soon forgotten, and accidents occur. Mining-safety Records The large employment and production concerned with anthracite contribute much to the mining-safety records of the mineral industry. Approximately 81,000 persons are. employed in this industry having mines concentrated in an area of 480 square miles in northeastern Pennsylvania. Because of the achievement of the anthracite industry in safety during 1948, the other branches of the mineral industry can profit by a study of what has been done to achieve that record. Where one mineral is produced by other large groups having methods of mining that are similar in many respects to the anthracite-mining methods, an achievement in such a large industry is important. Salient factors concerned with safetye in the anthracite industry are: no radical change has occurred in the mining-safety regulations pertaining to anthracite mines. Because anthracite mining is a branch of the coal-mining industry,

Jan 1, 1950

By Arthur Zentner

THE essentials of the electrolytic zinc process, as now used in commercial plants, date back to work done by Letrange in 1881. He used sulfuric acid to leach roasted sulfide and ,oxide ores, purified his solution very much as we do now, and electrolyzed the purified zinc sulfate solution. Ten years later Hoepfner developed a process using chloride solutions, and built three plants. One in England operated until 1924 in one of the works now merged in the Imperial Chemical , Industries, Ltd. Ashcroft built a plant in 1898 in the Broken Hill district of Australia. He used both chloride and sulfate solutions.. While his work failed, the aid his published results have been to later workers has made him an outstanding contributor to the de- velopment of the electrolytic zinc process. A good deal of work was done in the following years, aiming to electrolyze zinc chloride solutions and fused zinc chloride. Quite a bit of work on sulfate solutions was also done in the last years before the war. With the outbreak of the war, metal demand and rise in metal prices provided the stimulus which resulted in the remarkably rapid commercial development of electrolytic zinc. In this last period of development, all the work brought to commercial fruition has been with sulfate solutions. The high-density process, or the Tainton process, is used, as you know, in the Sullivan electrolytic zinc plant at Kellogg, Idaho, and will be used in the Evans- Wallower plant now being built at East St. Louis. The low-density process is used by the other plants now operating in the United States and other countries. There are now in operation and under construction four electrolytic zinc plants in the United States, two in Canada, two in Italy and one each in Australia, Rhodesia, Poland, Norway and Germany.

Jan 1, 1929

MR. Woo's succinct description of the mining and smelting of silver-lead in Mongolia, with the roasting-and-reduction process and cupellation, has much interest as a picture of methods that not only may have been in use, as he suggests, a thousand years ago, long before the existence of mining schools or chemical laboratories, but probably vary little, if at all, from the practice of prehistoric times, when King Priam's handsome silver vases, cups and bowls were formed. For it is highly improbable that such large objects were made from comparatively rare native silver, and the metal must have been smelted from ore, and most likely in great part from galena,, with cupellation of the lead. Dr. W. A. P. Martin, in his excellent book on the Lore of Cathay, points out that Chinese alchemy is over 2000 years old, antedating the European by at least six centuries; and he infers that the Chinese skill in metallurgy and many branches of practical chemistry owes its origin to " those early devotees of the experimental philosophy who passed their lives among the fumes of the alembic." Those alchemists, however, may have more likely derived some of their leading ideas from the mys terious, and at that time wholly unexplainable results observed in already very ancient metallurgical processes; in which, for example, certain stones were transmuted, as it were, into metals widely divergent in character from their ores, and even silver and gold were obtained from the most unlikely-looking mate rials. It is therefore, in any case, not improbable that the Chinese may have preceded western nations in the discovery of metallurgical methods. At all events, it is now evident that the Japanese acquired these arts from China, the former source of all their higher civilization. My own observation of old-fashioned silver-smelt ing at Hosokura, on the main island of Japan, and about 220

Jan 1, 1903

By T. B. Nolan, R. N. Hunt

In terms of present metal prices, analysis of extant records of the Eureka district indicate past production of the magnitude of $200,000,000 in recovered silver, lead, and gold. Production to date has been thoroughly oxidized ore from massive replacements, fissures, manta, and pipe-like bodies-in large part from the massive Eldorado (middle Cambrian) and Hamburg (middle to late Cambrian) dolomite horizons. In the productive area of about 6 square miles carbonate rocks comprise 80 per cent of the section, which includes early Cambrian to late Ordovician horizons. Four-fifths or more of the district's production came from a block of Eldorado dolomite in Ruby Hill that was moved in over younger horizons on strands of a regional thrust fault. The lower 500 to 600 feet of the block was much fractured and brecciated and became host to the ores. The Ruby Hill fault, a late normal fault, limits the Ruby Hill block of dolomite on the north for its entire length of nearly a mile and terminates the downward extent and exploitation of its ores. It introduced an hiatus of some 40 years in the district's development. Drilling of the past 20-odd years, followed by underground work, has now exposed the down-faulted extension of the Ruby Hill block of Eldorado dolomite and its contained ores, dropped 1800 feet in a dip shift to depths beneath the surface of 2000 to 3000 feet. The ores at depth are the sulfide counterpart of those mined in early years on the footwall side of the fault. The ores of the district may be attributed to the same source as the intrusive quartz diorite outcropping in a limited way south of Ruby Hill but found at depth elsewhere in drill holes. The long north-south axis of the district, its anticlinal structure, its major faults, and the distribution of the intrusives and, in their relation to the surface, the ores themselves, all suggest that erosion has not cut deep enough to expose the extent of intrusives and the ores consequent upon them.

Jan 1, 1968

Jan 1, 1953

By Frank W. Harris

The strength of hard drawn copper wire is a question of considerable importance to both manufacturer and consumer. Unlike steel and alloy wires, in which strength is governed by both chcniical and physical considerations, t,he high conductivity required for copper wire in the clcc-trical industry generally precludes the possibility of obt,aining tensile strength through the use of alloys. Consequently, this strenglh is largely a rnatter of the ~hysical structure, and all factors known to affect this structure, such as rolling temperature, die contours, lubricants, drawing speeds, etc., arc matters of prime importance. The experiments described here have becn carried out dl~ring the past year at the Baltimore plant of the American Smelting & Refining Co., in connection with a general investigat,ion of sorne of the questions mentioned above, with the object of studying thc physical ~t~ructure of hard drawn copper wire and the influence of ccrtain factors on t,hat st'ruct.ure. The work has been of an exploratory nature, rather than con~prehensivc., but it was thought that the result,s might prove of sr~fficient general interest tjo warrant their publicatlion. The bulk of the hard drawn coppcr wire used in places where strength is an important factor is rnanufacturcd to strict specification, based USU-ally in the United States on thab of t,he Arrlerican Society for Tcst'ing Materials (B-1-23). This specification calls for almost as high a, valuc of t,ensilc strength, consistent with elongation, as it is possible pract'icnlly to obtain, and only physically perfect mlaterial can be relied on to lliect such a specification. Obvious defects, such as laminat'ions protluc:etl through fins in bhe original rods or brittleness duo lo ovt~rdrawing, arc. usually recognized and need only passing refercncc. Laminatlions can be detected by twisting and untwisting the wircx several times; they will show up on the surface in the form of fins. Pig. 1 shows a very bad example of this defect. Thc wire may bc perfectly smooth before twisting hut, when such larrlinations arc3 prcstmt they will readily show up under this treatrncnt. This trouble is caliscd by sirriilar defects in the original rod produced by overfills in rolling. Fig. 2 shows the cross-section of the rod from which thc wire in Fig. 1 was drawn.

Sailing westward from the Society Islands in the fall of 1774, England's noted explorer Captain James Cook discovered New Caledonia-that long, linear island that has played such an important and varied role in the history of nickel. Upon his return to England the following year, Cook's announcement of this uncharted island generated governmental interest, but its distance from the Island Empire, the troubles in the colonies, and the difficulties with France combined to keep English interest indirect and in the background of the then-current events.

Jan 10, 1968

By Jay J. Burns

TWO zinc concentrating mills are operated by the St. Joseph Lead Co. in St. Lawrence County, N. Y. The Edwards mill is operating at present only sixteen hours a day treating 400 tons daily. The metallurgy at Edwards presents no unusual problems therefore this discussion is mainly limited to the metallurgy of the Balmat ore. The Balmat mill has a capacity of 1,250 tons per day and the operating crew consists of three shift bosses each with five millmen per shift. Two crusher operators work on each of two shifts and one cleanup man on day shift. The repair crew is made up of a foreman and three repairmen, one of the repairmen being capable of taking over any operating job in the mill from shift boss down. Each millman is capable of handling the next job in line and several men in the yard crew are broken into handling the start-off job in the mill so that temporary shortages of men do not cause extensive overtime. Sphalerite, pyrite, and galena, the principal ore minerals, occur in a gangue of calcite, dolomite, and silicates, especially diopside, plus tremo-

Jan 1, 1947

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 possible' 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 (subscale formation) 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' 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 detail 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 I-b 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 4o 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