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By Clarence E. Sims

DURING the past several years the steel casting industry has made studies of heavy castings in which the test bar has been taken from heavy sections rather than from attached or separately cast coupons. It has been noted that the ductility properties of these heavy sections are often lower than those normally expected. Such lowered ductility is usually accompanied by a spotty test bar fracture and the ductility values often can be greatly improved if a low-temperature aging treatment is given to the casting. A loss of ductility of this type is considered "abnormal," since it is not accompanied by an increase of tensile strength or hardness, and "temporary" when the ductility can be restored by aging. The cure of such an abnormal condition represents a real improvement in the quality of the steel. Some hundreds of previous investigations, largely qualitative in nature, have established beyond reasonable doubt that hydrogen is normally present in newly manufactured steel and that this gas, in small amounts, can cause a temporary abnormal loss of ductility. The commonly observed association of high gas content and low ductility has given strong evidence for the presumption that hydrogen, possibly assisted by other gases, is the primary cause of the low ductility observed. Accordingly, the Steel Founders' Society of America has, since Nov. 1, 1944, sponsored investigations at Battelle Memorial Institute whose primary objective is to obtain quantitative information on the relation of the amount of hydrogen and nitrogen in steel, together with associated methods of steelmaking and treatment, to low-ductility effects and porosity.

Jan 1, 1947

By J. B. Wagstaff, R. A. Buchanan, J. F. Elliott

High speed photography through blast-furnace tuyeres showed coke particles moving rapidly. Model studies showed a raceway was formed and gave quantitative results which were correlated with actual blast furnaces. Another study showed the similarity between hanging and the flooding of a packed column. This was explored by models. THE combustion zone before the tuyere in an iron blast furnace is a vital region because here are generated: 1—most of the gases on which the furnace depends to carry out its basic operation of reducing iron ore to the metallic state, and 2—the major fraction of the heat required in the nearby regions of the furnace for the various reduction reactions, the fusion of the slag, and the melting of the iron. Since the greater part of the coke is consumed in this region, the descent of the burden must be greatly affected by the characteristics of the tuyere zone. This region then would seem to be a profitable field for study. Fortunately, a view into this important zone is available to the operator through the tuyere peep sight. Here he sees relatively dark pieces of coke "dancing" in the blast. What he sees is of considerable help in interpreting the behavior of the furnace at a given time but the very rapidly moving particles and the intense radiation obscures what is happening very deep in the zone. This investigation was initiated in the hope that a better understanding of the combustion region could be obtained by using a high speed camera with a maximum speed of 3000 frames per sec. It seemed the best practical method of "slowing down" this characteristically violent action within the highly luminous field. Model studies and tuyere probing also have been used to aid in explaining the observed phenomena. Above the combustion zone, but below the fusion zone, there is probably a region in which the coke is comparatively stationary. Here are zones in which the gases must flow up through the granular bed counter to descending liquid slag and metal. There is no easy way to observe this zone in a blast furnace, but model studies have been of some help in explaining the nature of the zone and the laws governing the flow of the fluids involved. The whole problem is difficult and involved and any approach to a complete solution may require long investigation. This preliminary report has been written, therefore, because it is believed that appreciable progress has already been made that would be of interest to others. Tuyere Studies, Chemistry and Kinetics It is well known from the early work of Kinney and coworkers1,2 that combustion of carbon before the tuyeres appears to occur in two zones: Zone A: C + O, = CO2; AH77°F. = — 14,108 Btu per lb of carbon [I] Zone B: CO2 + C = 2CO; H77°F = + 6,183 Btu per lb of carbon [2] Zone A (Fig. 1) is close to the tip of the tuyere and zone B is somewhat farther back; there being a transition region in which both reactions occur. It is interesting to estimate the rate at which coke is burned before a tuyere with a wind rate of 90,000 cfm in a modern furnace having 18 tuyeres. Approximately 0.55 lb of carbon is consumed by eq 1 per tuyere per sec. A like amount disappears by eq 2 for a total consumption of 1.11 Ib per sec per tuyere. Assuming the coke is 85 pct C and has a bulk density of 30 lb per cu ft, this figure can be converted to a total of 1.30 lb of coke with a bulk volume of 0.043 cu ft disappearing per sec per tuyere. At the temperatures prevailing in the combustion zone (according to Kozlovich,³ he maximum is about 3400°F), the rate at which carbon is con-

Jan 1, 1953

By L. Sturkey

Quantitative X-ray diffraction studies of the precipitation of thorium in a Mg + 3.3 Th + 0.51 Zr alloy (HK31A) in both the as-cast and cold-worked states show that the precipitation may be described by f = 1 - e(t/T)1/2 over most of the aging period. The effects of cold work and temperature changes are determined. The precipitation of tile equilibrium Mg-Th compotund is Preceded by the formation of a transition phase of higher thorium content, with the cowposition Mg2Th and with a Laves-phase structure. Thorium-containing alloys of magnesium have assumed considerable commercial importance, especially for applications requiring exposures to temperatures greater than 500°F for appreciable lengths of time. The principal commercial wrought alloys in this system are HK31A, containing nominally 3 pet by weight thorium and about 0.7 pet by weight zirconium: and HM21A. containing 2 pet by weight thorium and 1 pet by weight manganese. These two alloys retain a high level of properties even after exposures of 100 hr at 600°F, while the more common alloys containing aluminum and zinc are badly overaged by these conditions. Therefore, in order to obtain some insight into the mechanism by which thorium produces high temperature stability in these wrought alloys, it seems desirable to investi- gate the effect of temperature and mechanical working on the precipitation processes involving thorium. Since the scattering power of a thorium atom for CuKa X-ray radiation is about ten times that for a magnesium atom, the magnesium alloys containing about 3 pet by weight thorium are ideal for quantitative measurements by X-ray diffraction of the amount of Mg-Th compound present at any time. Such quantitative measurements should be of theoretical importance in the study of the effects of time, temperature, and deformation on precipitation and precipitation hardening. Of the two commercial alloys, HM21A and HK31A, the latter is certainly the most suitable for study: In the Mg-Th-Zr2 system, only Mg-Th compounds need be considered, since no ternary compounds or binary Th-Zr3 and Mg-Zr4 compounds exist. The Zr is added to this alloy as a grain refining agent and probably plays a secondary role in precipitation. On the other hand. thorium and manganese form many

Jan 1, 1961

By James P. Dr. Kimball

SULPHUR is always present in mineral coal of every variety. In the oxidized state it may exist as sulphuric acid in combination with a base. In the unoxidized state it exists in combination with iron as bisulphide of iron. It is also supposed by some chemists to exist in unknown combinations with the organic elements of the coal. This supposition requires the demonstration as a fact that certain coals yield more sulphur than what may exist in a free state, or what belongs to recognized combinations, not only with the accompanying iron but with other inorganic bases abundantly occurring in coals, but which unfortunately are very rarely estimated. This practically as well as theoretically important question it is at present impossible to decide, simply for want of available thorough ultimate coal analyses including the ash. Such analyses, at the best imperfect, are laborious and intricate, and therefore seldom made, the much simpler proximate analyses, so-called, being resorted to by most chemists for technical purposes, and commonly substituted for more scientific work even in the laboratories of government surveys. And it is unfortunate enough that few ultimate analyses are extended to the composition of the ash, much less to its relation to the original constitution of the coal. Sulphur chiefly occurs in most coals in the form of yellow pyrites (pyrite) and white pyrites (marcasite), both minerals, characterized by differences in crystalline form and in physical properties as well as in color, but having the same chemical composition (FeS2). No coal is entirely free from one or both of these dimorphous forms of bisulphide of iron. It may be disseminated through the mass so as to be invisible, in plates or scales between the laminæ of the coal, or in conspicuous segregations or nodules, sometimes of considerable dimensions. Coals greatly differ as to the proportion of sulphur which they contain. They also differ as to the relative proportion in which its several forms of combination occur. Such qualitative and quantitative disparities are scarcely, if at all, more marked in separate coal seams of a uniform type than in different parts of one and the same coal seam, whether it be considered locally as constituted of several

Jan 1, 1880

By F. A. Champion

The work described in this paper was carried out in the Research Laboratories of the British Aluminium Company Ltd., under the general direction of A. G. C. Gwyer, Scientific Manager of the Company. In considering the effect of stress?corrosion conditions on metals, or the failure of metal through stress corrosion, it is evidently advisable to adopt a clear definition of the meaning of those phrases. There appears to be general agreement that stress-corrosion conditions may be defined as the continuous application of static stress to a metal while it is exposed to corrosive conditions, but recognition of the occurrence of true stress-corrosion in a metal is often a difficult matter giving rise to some confusion. For the purpose of this paper stress corrosion in a metal is defined as the acceleration of corrosion by the application of static stress. On this view it is necessary to test a metal not merely under stress-corrosion conditions, but also under the same corrosion conditions without the simultaneous application of stress, if the liability of the metal to stress corrosion is to be assessed. Failure of a metal under stress-corrosion conditions is sometimes quoted as evidence of stress corrosion (for example, by Althof(1)2), but this evidence is totally inadequate if the above definition is

Jan 1, 1945

By Robert Glass Cleland

[Incorporated under the laws of the State of New York OFFICE, 41) WALL STREET, NEW YORK 5, N. Y. Authorized4,000,000 shares $150,000,000.00 Outstanding-5,071,260 shares 126,781,500.00]

Jan 1, 1952

By E. O. Wagner, V. F. Parry, J. B. Goodman

The low-rank coals containing 10 to 50 pct natural bed moisture represent over half of the tonnage reserve of the available solid fuels of the United States, but only about 2 pct of United States coal production is derived from these fuels. Increased utilization of these large reserves will result if the bed moisture can be removed at the mine in high-speed low-cost processes. This paper presents a theoretical and experimental study of the factors affecting high-speed drying of coal dusts. The time required to heat particles of coal is proportional to the square of their diameter, and it is calculated that the probable time in minutes is equal to 6D2. In other words, a 1/16 in. coal particle should be heated to drying temperature in 1.5 to 2.0 sec. Likewise, 1/8 in. particles should be heated in about 6 sec. The net heat required to dry subbituminous coal and lignite varies from 240 to 375 Btu per pound, depending upon the moisture removed, and this heat can be obtained from 42 to 61 cu ft of hot gases at 600°F. The necessary heat also can be obtained from 7.5 to 11 cu ft of gas at 2000°F. A description of the design and operation of a pilot plant for flash drying coal dusts is presented. This plant dries 1/16 in. by 0 coal dust in suspension in 1.5 to 2 sec with 600°F gas at a rate of 1300 lb per hour per square foot of column area and operates continuously at an efficiency of about 85 pct. The design and operation of another pilot plant for drying 1/8 in. by 0 coal dusts Is also described. This unit dries coal in the fluidized state using the sensible heat of gases introduced at 2000°F and processes coal at a rate of about 1500 Ib per hour per square foot of grate area at 85 to 90 pct efficiency. Over 90 pct of the bed moisture of low-rank coal dusts can be removed by the methods described. The heating value of lignite can be increased 45 pet and that if subbituminous coal 25 pct in a few seconds. The physical and chemical properties of coal dusts before and after drying are presented in the report, and it is shown that the bulk density of the dried coal is equal to that of the raw coal. This phenomenon makes it possible to ship 25 to 45 pct more heat in a railroad car with consequent savings in freight costs. Introduction For several years the Subbituminous Coal and Lignite Section of the Coal Branch of the Bureau of Mines at Golden, Colo., has been concerned with upgrading low-rank coals by removal of natural bed moisture. These fuels contain 10 to 50 pct total moisture, which reduces their industrial value considerably. In 1938, investigations were initiated in cooperation with the University of North Dakota to study drying of lignite by the Fleissner process with heat derived from high-pressure saturated steam. Two pilot plants were built, and two reports were published giving the results of this work.l,2 It was demonstrated that lump lignite and subbituminous coal

Jan 1, 1950

By H. Y. Yancey, B. M. Bird

One of the problems studied by the U. S. Bureau of Mines in cooperation with the University of Washington has been the re-treatment of table middlings. Hydraulic classification has given the best results. Instead of using the classifier to prepare the feed to the tables, as has been the practice for many years in ore dressing, it is used to separate part of a middling product that cannot be re-treated successfully on the table. Middlings are desirable in a table plant because the separation according to specific gravity is incomplete; that is, in the products of the table there is always an overlapping of free particles of coal and refuse that can be distinguished with heavy liquids such as are used in the float-and-sink test. The causes of this overlapping may be divided into two groups, those outside the table separation itself and those inherent in the table separation. The first of these groups includes, among other causes, the following: (1) poor adjustments of the table, (2) overloading or underloading the table, (3) irregularities in the quantity and quality of the feed, (4) irregularities in the power and water supply, and (5) a vertical dancing motion of the table deck due to weak foundations. These causes of overlapping are largely unnecessary in a properly designed and constructed plant; but whenever they are present they materially affect the character of the middling product, and hence the problem of re-treatment. The other group includes three additional causes: (6) small differences in specific gravity between coal and impurities, (7) a size-specific-gravity relationship of the coal and refuse particles in the table feed such that the sizing action of the table opposes the separation according to the specific gravity, and (8) shapes of particles that prevent a separation. The sixth, small differences in specific gravity, may be a very important reason for an incomplete separation. The change in specific gravity from coal to shale is always gradual and the designation of one part as coal and another part as refuse is arbitrary. If some specific gravity, such as 1.45, is chosen as the dividing point between washed coal and refuse,

Jan 1, 1930

By H. S. Coe

ENGINEERS have long recognized the desirability of correlating the data obtained from small-scale slime-settling tests with commercial work as carried on in large tanks. This need, though most apparent in designing new installations, frequently arises also in existent plants, since a large range of experimental work can be performed without interfering with regular operation. GENERAL SETTLING PHENOMENA In order to develop rational methods of laboratory testing, it becomes necessary to study the general phenomena of settling. Since it was desired to give the public the benefit of these methods at as early a date as possible, together with the knowledge of the general principles of slime settling necessary for a clear understanding of the laboratory tests, we have ventured to discuss the subject in so far as brought out by the work which we now have under way. We realize that certain of our preliminary conclusions may be subject to modification, but it seems probable that, with but few exceptions, the general laws enunciated will cover the settling behavior of all pulps encountered in metallurgical plants. However, it must be recognized that there is still a vast amount of work to be done upon certain phases of the subject; therefore, at this time we will attempt only a discussion of the behavior of ore pulps during the process of settling or dewatering, under certain given conditions. The laws and principles controlling these conditions are not fully established, so that a complete discussion of them will not be attempted in this paper. In metallurgical practice, slime pulp consists of water, finely divided sand

Jan 3, 1916

By AIME AIME

THANKS to the excellent preliminary work of: the Division officers and the local committee the fall meeting of the Coal Division at Bluefields was a brilliant success. West Virginia was at its best with its beautiful mountains, good roads and foliage, just beginning to turn to autumn colors. The meeting began on time and was kept on time throughout. The papers were-well prepared and, being on subjects of live interest, provoked 'lively discussion. One factor in bringing this about was that they were not too numerous and that with one exception copies had been submitted in advance a sufficient time to permit of them having been studied. The Friday morning session was presided over by John .J. Lincoln of the Crozier Coal and Coke Co. and president of the Pocahontas Coal Operators Association. After brief announcements by Thomas H. Clagett, chairman of the local committee, regarding plans for the two day's involved, and by Howard N. Eavenson, chairman of the Division, the reading of papers was taken up.

Jan 1, 1931

By J. A. Herbst, K. Rajamani, M. Siddique

This paper presents an investigation of the accuracy of population balance model predictions for ball mill scale-up. Experiments performed in 25.4 x 29.2 cm (10 x 11.5) batch mill are used to estimate linear grinding rate parameters that, in turn are scaled according to specific power draft to predict performance in 381 x 292 mm (15 x 11.5 in.) and 762 x 457 mm (30 x 18 in.) batch and continuous ball mills, respectively. Results are presented for wet and dry grinding of two homogeneous solids, limestone (soft) and quartz (hard), and one heterogeneous solid, a complex molybdenite ore. In all cases good agreement between predicted and experimental product size distributions was obtained.

Jan 1, 1983

By A. S. Michaels, M. C. Porter, A. Stancell

Previous laboratory studies have demonstrated that the injection of small quantities of reverse wetting agents during water displacement can increase oil recovery from unconsolidated porous media.9 In the present investigation, an attempt has been made to determine more fully the effects of reverse wetting treatments and to clarify the mechanism by which increased oil recovery is effected. Water-oil displacements were performed in beds of 140-200 mesh silica sand. Hexylamine slugs (injected after 0.25 pore volume of water throughput), when adequate in size and concentration, were effective in promoting additional oil recovery. Their effectiveness increased with the quantity of amine injected. However, slugs of sufficient size and concentration to stimulate oil production at water flow rates of 34 ft/day did not do so at 4 ft/day. Visual studies in a glass grid micromodel have shown that the stimulation of oil production, via ayueous hexylamine, is a result of transient changes in the oil wettability of the pore walls. if the amine slug is of sufficient size and concentration to induce significant changes in the adhesion-tension, large continuous oil masses will be formed. if the superficial water velocity is high enough to result in rapid desorption of the amine, a favorable "wettobility gradient" may be established across the masses; under such conditions, high oil mobility is observed, and increased oil recovery results. INTRODUCTION It is generally agreed that the efficiency of oil displacement by water in porous media is limited in part by capillary forces which cause the retention of isolated masses of oil — resulting in the so-called "irreducible minimum oil saturation". Recent estimates10 indicate that there are about 220 billion bbl of petroleum in United States reservoirs which are not economically recoverable with present techniques (such as water flooding). This amounts to almost five times the known recoverable reserves. It has been recognized for some time that a suitable alteration in the water-oil interfacial tension and/or the contact angle, as measured between the water-oil interface and the solid surface, should result in better displacement efficiency. Surface active agents can be used as interfacial tension depressants to accomplish this objective,1,2,7 but unfortunately, the additional oil recovery is seldom commensurate with the treatment cost. In contrast to interfacial tension depressants, the effect of contact angle alterations on water-oil displacements has received relatively little attention in the literature. It is known that the wettability affects the displacement process.3,4,11 Displacements in water-wet systems generally result in lower residual oil saturations than those in oil-wet systems. The effect of "'transient" wettability alterations concurrent with the displacement process have been investigated by Wagner, Leach and coworkers,4,11 wherein it has been demonstrated that the establishment of water-wet conditions during water flooding of oil-wet, oil-saturated porous media is accompanied by significant increase in oil displacement efficiency. Michaels and Timminss studied the effects of transient contact angle alterations resulting from chromatographic transport of reverse wetting agents through unconsolidated sand. It was demonstrated that chromatographic transport of short-chain (C4 through C8) primary aliphatic amines can improve oil recovery and that the recovery increases with the quantity of amine injected (i.e., with either the amine concentration or the volume of the slug injected). Circumstantial evidence indicated that the increased displacement efficiency resulted primarily from transient changes in wettability of the porous medium. In the Present investigation. additional information has been obtained on the effects of reverse wetting treatments and the mechanism by which increased oil recovery is accomplished. Hexylamine slugs of varying size and concentration were chromato-

Jan 1, 1965

By L. F. Reinartz

FROM the earliest times when our prehistoric ancestors laboriously fashioned crude tools and weapons from meteoric iron until our day when we manufacture steel in 150-ton open-hearth furnaces, the production of iron and steel has played a dramatic and important role in the development of civilization. Progress in the science of refining iron ore into iron and steel was painfully slow for many centuries. The keen scimitars of Damascus, the broadswords of the English knights, the coats of mail of French knights, and the Iron Pillar of Delhi are well¬known examples of medieval metallurgical technique. Expense and the scarcity of raw materials originally limited the distribution of iron and steel products. It was not until the nineteenth century that a determined effort was made to adapt the use of steel to peaceful pursuits. The spectacular and rapid strides made in the manufacture of steel during the last hundred years were hastened by the invention during the decade 1860 to 1870 of two great steelmaking processes-the Bessemer and the open-hearth process.

Jan 1, 1936

By C. A. Czako

INTRODUCTION In recent decades sintering and pelletizing of finely divided materials have become the primary tonnage producing modes of agglomeration. This statement is especially true in the iron and steel industry and, to a lesser degree, in the nonferrous, chemical and non-metallic minerals processing industries. In every industry the main objectives in agglomerating fines are essentially the same, namely to convert ores, minerals and chemicals of undesirable fineness into agglomerates characterized by a size consistency desirable for subsequent use or processing. Depending on the type of agglomeration process selected and the conditions maintained during agglomeration, the physical process of increasing size is complemented by a number of other unit processes. These processes can occur simultaneously, consecutively or in an overlapping manner. Some of these additional unit processes are incidental to the agglomeration operation, but at the same time can be critical, depending upon the subsequent use of the product. Accordingly, during processing, conditions have to be controlled to either suppress or enhance the extent of completion of these unit processes. The purpose of this report is to review laboratory testing as the basis for engineering modern sintering and pelletizing plants. Considering that most typical applications are for the iron and steel industry, agglomeration of ferrous materials is reviewed and discussed. When these total processes are adapted to suit non- ferrous materials, chemicals, or non-metallic substances, the over- all approach remains the same; only the processing parameters are affected as necessitated by the different nature of the materials.

Jan 1, 1977

By C. A. Mitke

The United Verde Extension mine is located in the Jerome mining district, on the eastern slope of the Black Hills, approximately northeast of the town of Jerome, Yavapai County, Arizona. The ore deposit may be termed a replacement in Yavapai schist. This schist is one of the oldest formations in the district, being probably of volcanic origin, and has been folded and faulted and contains intrusions of diorite and quartz porphyry. It is believed that the mineralization followed the porphyry intrusions and replaced the country rock; this was followed by erosion and a period of secondary enrichment, all completed in pre-Cambrian time. Later sediments of sandstones and limestones, to the depth of approximately 600 ft. (182 m.), were laid down, followed by volcanic flows. Faulting and erosion again took place, resulting in the present complicated arrangement of the strata. Prospecting, therefore, is very difficult, because the sediments practically cover the mineralized areas. This necessitates the sinking of deep shafts, cross-cutting, and, in some instances, diamond drilling to learn something of the various relations of the different formations and the occurrences of intrusions associated with ore deposition. The locating of new orebodies, therefore, is beset with innumerable difficulties. EARLY MINING METHODS The two orebodies constituting the principal resources of the company are known as the small orebody and the Bonanza, or large orebody. These are about 150 ft. (45 m.) apart, and while they appear to be distinct orebodies may later prove to be connected. The character of the ore, the general associations of the porphyries adjoining the orebodies, and other characteristics, both in the ore and general environment, are very similar. The small orebody was the fist to be discovered and was mined for some time before the Bonanza was found. At first, a large amount of ore was extracted by means of development work, but as the smelters treating this class of ore were located from 60 to 400 mi. (96 to 643 km.) away, only the highest grade yielded a fair profit and it became necessary to do selective mining. The main workings

Jan 1, 1920

GENTLEMEN Submitted herewith are the report of the Treasurer for the year 1938 and reports for the same year of the following standing committees: Admissions, Membership, Papers and Publications, Mining and Metal¬lurgy (Magazine), Library, Speakers for Local Sections and Student Societies, and Student Relations. To these reports members are referred for further details. Membership.-The end of the year 1938 saw Institute membership at an all-time peak: 12,474, made up of 2898 Student Associates and 9576 members of other classifications. The next highest level had been reached at the end of 1921 when corresponding figures were: total, 10,329; student members, 1450; all other classifications, 8879. The net gain for the year was 1495, of which 751 were Student Associates and 744 in the other categories. Two factors contribute to the growth of membership: (1) the enrolment of new members; and (2) the retention of members already on the roll as reflected in a relatively small number of resignations and suspensions for nonpayment of dues. For the first, much credit goes properly to the general Membership Committee that functioned for a second year under the chairmanship of Clyde E. Williams. With the cooperation of Institute members in general, to whom Mr. Williams expresses appreciation in his report, the Committee has been successful in acquainting eligible nonmembers with the purposes, activities and advantages of the Institute. The result has been the receipt during the year of 1162 applications, exclusive of Student Associates. This compares with 1212 during 1937 and 1266 during 1936. However, in considering this modest decline, account must be taken of the somewhat less prosperous conditions prevailing in the mineral industries and, consequently, among engineers engaged ?in those industries.

Jan 1, 1939

By W. C. Clarke

An empirical study of the nature of the embrittle-ment which occurs in martensitic and semiaustenitic precipitation hardening stainless steels upon exposure at temperatures of from about 550" to 875°F has been undertaken. This work was aimed at determining cazusation and means of controlling this phenomenon. A commercial copper bearing precipitation hardening alloy was used as a basic material for study. The effect of heat treatment variables was studied as was the effect of variations in analysis. It is concluded from the evidence that martensitic and semiaustenitic precipitation hardening stainless steels are subject to 885°F ernbrittlement similar to that observed in the straight chromium stainless steels. A characteristic of precipitation hardening stainless steels which has limited their use in certain applications is that they embrittle when held at temperatures in the range of from about 550" to 900°F. This is true to a more or less degree in all currently available alloys, either the basically martensitic type or the semiaustenitic type. The rate of embrittlement varies markedly with exposure temperature, being low at 550" to 600°F and in-creasing as the temperature increases. In spite of this embrittlement, these alloys with their unique combination of high mechanical strength, reasonable toughness, and good corrosion resistance are used in many hundreds of applications. Nevertheless, there are potential applications where the embrittle-ment described is a limiting factor. The purpose of this investigation was to study the embrittlement of these alloys and to find a way to control or eliminate it. GUIDELINES USED IN PRESENT WORK The work reported in this paper is based on a study of 17-4 PH*, a very widely used alloy. It has been used *Trademark of Armco Steel Corp., licensor. in pressurized water and boiling water atomic reactors operating at about 550°F for a number of years. As the life of such equipment is extended or operating temperatures are raised, the possibility of embrit-tlement becomes of increasing concern to materials engineers. Much investigation work was done with respect to the use of 17-4 PH at 550°F. K. C. Antony' states "Such estimation" (of an activation energy for the diffusion of chromium in iron) "would indicate W. C. CLARKE, Jr. is Senior Research Engineer, Advanced Materials Division, Armco Steel Corp., Baltimore. Md. This manuscript is based on a talk presented at the symposium on New Developments in Stainless Steel, sponsored by the IMD Corrosion Resistant Metals Committee, Detroit, Mich., October 14-15, 1968. significant secondary aging is improbable at temperatures less than 700°F within normal component service life". This statement is modified however by the recognition of the accelerating tendencies of applied stress and internal stress as well as the possible effect of irradiation. In this investigation of 17-4 PH, the H 1100 (1900°F-1 hr oil quench or air cool + 1100°F-4 hr-air cool) condition was used, partly because this condition is normally used in atomic reactors. As shown later, the precipitation hardening temperature has no real bearing on the rate of embrittlement. An exposure temperature of 800°F was selected since embrittlement at 800°F is rapid, permitting development of relative data in time periods of 400 to 500 hr. For those not familiar, a nominal present day analysis of 17-4 PH is: C Mn P S SiCrNiCuCbN 0.04 0.30 0.015 0.015 0.60 16.00 4.30 3.25 0.23 0.030 TYPICAL BEHAVIOR OF 17-4 PH Figs. 1 and 2 show the behavior of a commercial heat of 17-4 PH under the conditions defined. Characteristically, 800°F exposure causes a rapid drop in Charpy V-notch impact strength. Tensile and yield strengths gradually increase and a gradual loss of elongation and reduction of area occur, accompanied by an increase in hardness. Notched tensile strength increases to 125 hr exposure and then sharply decreases after exposure for 500 hr. The notched vs un-notched tensile ratio remains virtually constant to exposure for 125 hr (1.67 to 1.56) but drops to 1.15 after 500 hr. Tensile ductility is not alarmingly affected even after much longer exposure times than these. For example, samples aged at 1100°F for 1 hr exposed at 800°F for 4000 hr showed a drop in elonga-tion of from 13 to 11 pct and in reduction of area of from 58 to 37 pct. Notched impact is the property SmIgth KSI 3JJ[/__________^UTS-Nrteh 260 ;/- 240 —^ 200 UTS-Smooth________._, o ioo mo Sob" m Too Hours Exposure Fig. 1—Effect of exposure at 800°F for various times on notched tensile strength and smooth tensile and 0.2 pct yield strength of 17-4 PH in the H 1100 condition.

Jan 1, 1970

By T. R. Graham, R. S. Dean. J. R. Long

Although considerable information has been published concerning manganese additions to the aluminum bronzes, these data refer principally to the two-phase alloys containing 8 to II pet aluminum, with some incidental information on the single-phase alpha solid solution alloys. Straussl gives an excellent review of the literature on aluminum bronzes up to 1927 and a bulletin2 of the Copper Development Association brings the bibliography up to 1938. The most extensive work on manganese addition is that of Rosenhain and Lantsberry,3 who investigated alloys ranging up to 10 pct aluminum and up to 10 pct manganese, and presented data on the physical properties of sand-cast, chill-cast, and several wrought alloys. The greater portion of the work, however, concerns alloys ranging from 7 to 10 pct aluminum in the cast condition and sheds little light on the properties of wrought single-phase alloys. Corson4 notes that alloys containing 10 pct manganese and 4 pct aluminum are not hardenable by heat-treatment, while one with 15 pct manganese and 5 pct aluminum can be hardened, but he gives no tensile data on it. In fact, no systematic study of the properties of single-phase wrought alloys containing substantial amounts of manganese has been reported. It should also be noted that most of the investigators worked with alloys containing significant amounts of iron and silicon, and that these impurities, whether intentionally added or accrued from the raw materials used in the preparation of the alloys, may be expected to have a direct bearing on the resultant properties. In the work on alloys made with electrolytic manganese, the Bureau of Mines has undertaken an investigation of the copper-manganese-aluminum system for the purpose of establishing the constitution and properties of high-purity alloys. In a recent paper6 the authors reported a metallographic investigation of the alpha solid solution area and the adjoining fields of the copper-manganese-aluminum system up to 50 pct manganese. This study established the alpha-phase boundaries at 50" temperature levels from 400' to 850°C. It was found that the addition of manganese to copper-aluminum alloys decreases the solub%ty of aluminum in the alpha phase (Fig I), curving the boundary toward the copper-manganese base line. The greatest change occurs in the first 20 to 25 pct manganese, which decreases the solubility of aluminum to approximately 4 pct. With larger amounts of manganese the alpha boundary tends to parallel the copper-manganese binary. At 13oo'F and higher,

Jan 1, 1947

By R. S. Dean. J. R. Long, T. R. Graham

Although considerable information has been published concerning manganese additions to the aluminum bronzes, these data refer principally to the two-phase alloys containing 8 to II pet aluminum, with some incidental information on the single-phase alpha solid solution alloys. Straussl gives an excellent review of the literature on aluminum bronzes up to 1927 and a bulletin2 of the Copper Development Association brings the bibliography up to 1938. The most extensive work on manganese addition is that of Rosenhain and Lantsberry,3 who investigated alloys ranging up to 10 pct aluminum and up to 10 pct manganese, and presented data on the physical properties of sand-cast, chill-cast, and several wrought alloys. The greater portion of the work, however, concerns alloys ranging from 7 to 10 pct aluminum in the cast condition and sheds little light on the properties of wrought single-phase alloys. Corson4 notes that alloys containing 10 pct manganese and 4 pct aluminum are not hardenable by heat-treatment, while one with 15 pct manganese and 5 pct aluminum can be hardened, but he gives no tensile data on it. In fact, no systematic study of the properties of single-phase wrought alloys containing substantial amounts of manganese has been reported. It should also be noted that most of the investigators worked with alloys containing significant amounts of iron and silicon, and that these impurities, whether intentionally added or accrued from the raw materials used in the preparation of the alloys, may be expected to have a direct bearing on the resultant properties. In the work on alloys made with electrolytic manganese, the Bureau of Mines has undertaken an investigation of the copper-manganese-aluminum system for the purpose of establishing the constitution and properties of high-purity alloys. In a recent paper6 the authors reported a metallographic investigation of the alpha solid solution area and the adjoining fields of the copper-manganese-aluminum system up to 50 pct manganese. This study established the alpha-phase boundaries at 50" temperature levels from 400' to 850°C. It was found that the addition of manganese to copper-aluminum alloys decreases the solub%ty of aluminum in the alpha phase (Fig I), curving the boundary toward the copper-manganese base line. The greatest change occurs in the first 20 to 25 pct manganese, which decreases the solubility of aluminum to approximately 4 pct. With larger amounts of manganese the alpha boundary tends to parallel the copper-manganese binary. At 13oo'F and higher,

Jan 1, 1947

By David T. Peterson

Calcium metal was found to deoxidize thorizcm at 1000° to 1200° C. The reaction kinetics were determilled and related to the diffusion coefficients of oxygen in thorium. The solubility of oxygen in thorium, the minimum oxygen concentration, and the diffusion coefficient were determined from 1000° to 1200°C. This firocess results in the lowest oxygen concentrations zohich have been reported for thorium metal. FOR many years it has been known that calcium metal will reduce thorium oxide to thorium metal. This reaction has been the basis for several methods of preparing thorium metal. From the equations giv-by Kubaschewski and vans, ' AF" for the reaction Cao, + Tho,(,) - CaO(,, + Th(,) was calculated and found to be -3.4 kcal at 1000°C, -2.5 kcal at llOO°C, and -2.0 kcal at 1200°c. Thorium is very slightly soluble in liquid calcium, and the solubility of calcium in solid thorium is very low. Consequently these metals would be in essentially their reference states. If thorium containing oxygen were equilibrated with liquid calcium between 1000° and 1200°C, the oxygen content of the thorium would have to be below the solubility limit in thorium. Oxygen is one of the impurities most difficult to remove from thorium and is the most abundant impurity in metal prepared by almost all known methods. Fortunately, oxygen does not have a large influence on the properties of thorium because the solubility in solid thorium is very low. EvenT in thorium containing 100 ppm of 0, particles of thorium oxide can be observed in the microstructure. In view of the incompatibility of thorium oxide and liquid calcium and the low solubility of thorium oxide in thorium, the deoxidation of thorium by this method was investigated. For thorium containing an amount of oxygen well in excess of the solubility limit, the reaction should proceed in the following sequence. The oxygen content of the thorium matrix near the surface would be depleted by the diffusion of oxygen to the surface. At the surface, the oxygen would react with calcium to form calcium oxide. To maintain equilibrium within the thorium, thorium oxide would dissolve to keep the matrix saturated. Consequently, the thorium-oxide particles would disappear first at the surface and then the particle-free rim would grow in thickness. If the rate-controlling step were the diffusion of oxygen through this layer of thorium which was growing in thickness in direct proportion to the amount of oxygen removed, the well known parabolic time law should be observed. If the oxygen concentration at the surface of the thorium and at the inner surface of the deoxidized rim were known, the diffusion coefficient of oxygen in thorium could be calculated from the parabolic rate constant. EXPERIMENTAL PROCEDURE The thorium metal used in this study was prepared by calcium reduction of ThF, by the method described by Wilhelm.' The analysis of this metal is given in Table I. The carbon was determined by combustion, the oxygen by the HC1-insoluble residue method, nitrogen by the Kjeldahl method, and the other elements by emission spectroscopy. A section of this ingot was hot rolled at 600°C to 1/4 and 1/8-in. thick plates. Specimens approximately 7/8 in. square were cut from these plates, and all surfaces of the specimens were cleaned and smoothed by filing with a clean file. Individual specimens were placed in 1-in. diam by 2-in.-long tantalum capsules. Approximately 1 g of clean, high-purity calcium was placed in the capsules and an end closure arc-welded in place. The tantalum capsules were sealed in Inconel crucibles to protect the reactive metals from oxidation. The entire loading procedure was done in a glove box filled with pure argon. The loaded crucibles were placed in a muffle furnace, controlled within 2OC of the desired temperature, for a measured length of time. After the specimen had cooled to room temperature, it was sectioned perpendicular to the large faces and through the mid-point of two of the sides. The sectioned specimen was mounted and polished through Linde A abrasive. The rim which was free of thorium-oxide particles could be clearly observed microscopically as mechanically polished. Twenty measurements of the thickness of the rim were made at equally spaced points far enough from the end of the

Jan 1, 1962