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By D. K. Deardorff, Earl T. Hayes

An improved technique is described for the accurate determination of melting points of metals in the temperature range 1500' to 2500°C. The improvements consist of gradient heating and refinements in cavity preparation to obtain true black-body conditions. The melting point of hafnium, as determined by this method, is set at 2222°±30°C. This is over 200°C higher than one of the values reported earlier. Discrepancies in the previously reported values for the melting point of hafnium are explained. The melting points of zirconium and titanium are found to be 1855O±15OC and 1668°±10°C, respectively. Reproducibility of results was ±3OC. PRIMARILY, this report is being made to correct a 1975o±25oC1 value for the melting point of hafnium, and to present an improved method for melting point determination. As a matter of interest, the technique was also applied to determining the melting point of zirconium and titanium. There is a wide difference in the melting point of hafnium as reported by competent investigators. DeBoer and Fast' reported a value of 2230°±500C, and later work of McPherson, as reported by Aden-stedt, placed the melting point at 1975o±25oC. Zwikker" calculated that the melting point was 2430°C. In resolving this discrepancy, improvements were made in the procedure for determining the melting points of refractory metals in the range 1500" to 2500°C. Special techniques are necessary to determine the melting point of these metals accurately. Since the metals oxidize in air above 900oC, the determinations must be carried out in an inert gas or vacuum. Also, every known refractory contaminates them to some extent. In addition, the attainment of true black-body conditions is always difficult. DeBoer and Fast actually determined the melting point of Hf-Zr as-deposited iodide process alloys and extrapolated to 100 pet Hf. McPherson employed a tungsten wire suspension similar to that described by Schramm, Gordon, and Kaufmann,1 and used hafnium metal produced by the iodide process. There was no apparent reason for the wide spread in melting points, since the quality of the metal was very good and the work was under the direction of highly competent investigators. Retracing some of this work revealed one understandable error in the case of hafnium, and led to development of an improved technique for determining melting points of reactive metals in the range 1500" to 2500°C. Material Crystal bar hafnium, zirconium, and titanium were used for this work, with analyses as shown in Table I. The hafnium was of the highest purity that has been prepared, though not as pure as the zirconium and titanium. At the instigation of the Pittsburgh Area Office of the AEC, a special lot of Hfo2 was purified, converted to the tetraflouride, and bomb-reduced with calcium, all at the Iowa State College Laboratories. This crude hafnium metal was then refined by the iodide process at the Foote Mineral Co. All specimens were cut with a Sic wheel, ground, pickled, and dried carefully before use. Procedure General Tungsten Suspension Method—In this method, a small specimen is suspended by a fine tungsten wire in a slender, induction-heated tungsten or tantalum cylinder, all under vacuum. The melting point is determined by heating the specimen slowly while observing it with an optical pyrometer focused upon a portion of the specimen that radiates as a black body. This means that there should be no reflected radiation, either from colder objects near the pyrometer or from hotter surfaces. The induction heater would be the only hotter object and, if it is slender enough, the specimen will attain the same temperature. Often a slender hole is drilled into the specimen as a source of black-body radiation. This was the general method used by McPherson in obtaining his value of 1975°C for the melting point of hafnium. In trying to repeat this work, it was found that the points of contact between the

Jan 1, 1957

By Harrison Schmitt

DURING the past decade the writer has studied and mapped certain ore deposits and their structural associations in the states of Chihuahua, Durango, New Mexico and Arizona, and he believes that these deposits, with the exception of the manto-chimney, are representative of the principal types in the area of the states named. In this paper the deposits are described; then generalizations are drawn so far as seems appropriate. HANOVER, NEW MEXICO The Hanover; New Mexico, zinc deposits were briefly described by Lindgren and others,1 Paige2 and recently in more detail by Schmitt.3 These, the kind ordinarily called contact metamorphic, border the southern end of an oval area of granodiorite intrusive 3/4 mile wide and 2 1/2 miles long (Fig. 1). The granodiorite has intruded, folded, and metamorphosed sedimentary and igneous rocks, which range in age from pre-Cambrian to Upper Cretaceous. About 90 per cent of the ore has replaced coarse, recrystallized, pure, fossiliferous, lower Mississippian, nonmagnesian limestone (Hanover limestone) 110 ft. thick;4 about 75 per cent of it occurs in the upper 50 ft. of this horizon just below an 18-ft. lower Pennsylvanian shale bed, which lies on a locally inconspicuous unconformity representing upper Mississippian time. The orebodies show five shapes or attitudes, each dependent on a special structural situation: 1. Most of the ore occurs as podlike; thick lenslike or other "three-dimensional" shoots extending from top to bottom of the Hanover limestone and lying adjacent to the outer contact of a silicate zone largely of andradite, which follows the intrusive contact (Figs. 1 and 2).

Jan 1, 1933

By Porter W. Shimer

(New York Meeting, February, 1912.) IT does not seem to be generally known that some American pig-irons contain notable amounts of vanadium, and while the present investigation is far from covering the whole range of irons, it is hoped that, at least, it may serve to call attention to the importance of looking for this element. The majority of the pig-irons investigated were made in the Lehigh Valley and neighboring furnaces, using more or less New Jersey magnetite in their mixtures. Many of these ores, and probably all of them, contain a little vanadium as well as titanium; the ore from one of the largest of these mines contains 0.05 per cent. of vanadium and 0.60 per cent. of titanium. Dr. Thomas M. Drown was the first to detect the presence. of vanadium in the incrustations 1 occurring on certain pig-irons, and he also found this element in a number of magnetites, but the methods for its accurate determination had not, at that time, been well worked out. In a general way, it may be said that the Lehigh Valley pig-irons contain from 0.02 to 0.05 per cent. of vanadium and from 0.10 to 0.20 per cent. of titanium. These elements follow the silicon; that is, the furnace-conditions which produce a high-silicon, low-sulphur iron will cause the maximum reduction of vanadium and titanium, and the lower grades of iron, with low silicon and high sulphur, have a lower content of these elements. The following analyses of irons made from the same mixture, but under varying furnace-conditions, show this very well Vanadium. Silicon. Sulphur. Per Cent. Per Cent. Per Cent. NO. 1 X, . . . 0.042 3.46 0.022 No. 2 plain, . . 0.038 2.26 0.041 Mottled, . . . 0.0'29 0.52 0.106 1 Robertson and Firmstone, Note Concerning Certain Incrustations on Pig Iron,Trans., xii., 641 (1883-84).

Aug 1, 1912

By AIME AIME

AMONG the recent mining and metallurgical developments in England great interest has been shown in the development of an iron-ore field covering 26,0.00 acres in Northamptonshire, containing 500,¬000,000 long tons of ore; and the erection at Corby, by Stewarts & Lloyds, of a modern basic bessemer steel plant and tube works. The entire project was planned to cost about £3,300,000. Many improvements have been made in the varied equipment that is being installed, some of which has set mew records for massiveness. There is, for instance, a new roll crusher, which has been manufactured by Hadfields, Limited, of Sheffield, the largest ever built in England, and weighing 130 tons. This machine, shown in Fig. 1, as erected at the Hadfields shops, is primarily designed to take blocks of iron ore as they come from the steam shovel. The maximum size is 54 by 48 by 36 in., hut occasional pieces slightly larger than this may be accommodated. The capacity is upwards of 500 tons per hour, the product passing to a secon-

Jan 1, 1934

By Cleland N. Conwell

Coals are found in all parts of Alaska, ranging in geologic age from Carboniferous to Tertiary, and grading from lignite through anthracite. Only the Matanuska and Nenana coal fields have been extensively developed. Nenana Field Today roughly 94% of the coal mined in Alaska comes from the Nenana field near Healy. The coal-bearing horizons in the Nenana field are found in a sedimentary sequence of Tertiary age approximately 2800 ft in thickness. The sediments rest directly on schists of possible Precambrian age. Individual coal beds in the field have been designated by both letters and numbers, starting with the alphabetical designations from A to G, and the numbers 1 to 6. Of these coals, the principal beds that are mined are F, 1, 2, and 3. These vary greatly in thickness, e.g., bed 1 ranges to over 50 ft, and beds 2 and 3 to 30-40 ft.

Jan 10, 1972

By C. E. Birchenall, C L. McCabe

IN attempting to extend vapor pressure measurements of the type previously reported by Schadel and Birchenall1 for silver and by Schadel, Derge, and Birchenall' for silver-silicon to other systems, it was observed that the materials melted at indicated temperatures 10" to 15" below their accepted melting points. Further investigation revealed that the thermocouple readings were in error due to appreciable conduction losses along the reference thermocouple wires. If the wire diameter of the reference couple inserted into the Knudsen cell was reduced, the correction for the indicating couple changed in a manner tending to explain the melting behavior. When extrapolated to zero wire diameter from measurements with several reference thermocouples of different wire thickness, the melting point of silver then agreed with the indicated temperature at which silver chips were observed to coalesce into a sphere. Approximately the same calibration was given by observing the melting of small wires of silver or gold in the Knudsen cell connected in series with an ammeter, where the leads into the cell were very fine in order to minimize heat conduction. Unfortunately neither of these methods seemed to yield a sufficiently precise temperature calibration to match the apparent precision of the other aspects of the vapor pressure measurement. It was decided. therefore, to redetermine the vapor pressure of silver in another setup under conditions permitting precise temperature measurement. The vapor pressure of pure silver could then be used as an internal calibration of temperature in the older unit in making runs on alloys. This has been done; the present report is a correction to ref. 1. Experimental Procedure The apparatus, shown in Fig. 1, was very similar to that employed by Harteck,3 except that the orifice sizes were smaller and the residual pressure in the vacuum system was probably much lower. A small, sharp-edged hole, nearly circular in shape, was ground into the rounded end of a quartz tube. The orifice area was then measured by tracing the image at known magnification on graph paper and counting the squares enclosed. The silver specimen was sealed into the tube to make a Knudsen cell. A tantalum jacket surrounding the cell served to increase the uniformity of temperature. This assembly was placed in the bottom of a long quartz tube with an inside diameter of about 1 in., which was connected to the vacuum system through a ground joint sealed with picein wax well removed from the furnace. A thermocouple tube inserted through the top of the vacuum line reached into the tantalum jacket so that the thermocouple junction was immediately adjacent to the Knudsen cell except for the protection tube wall. A resistance furnace could be raised to cover the end of the quartz tube containing the cell in such a way that the cell was in the uniform temperature zone 13 in. from the end of the furnace. An ionization gage was included in the vacuum system in the cold lines of wide diameter, immediately beyond the ground joint. The vacuum system consisted of a mercury one-stage diffusion pump, backed by a Welch duo-seal mechanical pump. The pumps were separated from the reactor chamber by a dry ice trap. The ionization gage always read less than 10-5 mm Hg after initial outgassing and before each run was started. Each newly filled Knudsen cell was evacuated at high temperature overnight before the first weighing was made. The cell was returned to the system, heated for a measured time at constant temperature, cooled, and reweighed. The heating and cooling times were quite short since the hot furnace was raised to receive the reactor at the beginning of the run and removed again at the end. The tube heated or cooled quickly. The total mass loss was attributed entirely to effusion of silver vapor from the quartz cell, since empty quartz cells maintained constant mass through similar heating cycles. The vaporized silver condensed on the cold walls of the quartz tube extending above the furnace. Earlier studies in the induction heated unit had shown that the same vapor pressure was found for silver, whether the silver was in contact with the tantalum metal cell or with porcelain or quartz liners. The Pt-Pt-10 pct Rh thermocouple was calibrated against a secondary standard of the same material and found to agree with the published tables. Always operating in air at temperatures below 100O°C,

Jan 1, 1954

By A. M. Gaudin

This year the American Institute of Mining, Metallurgical and Petroleum Engineers has chosen to give me its Robert H. Richards Award, a distinction which is widely regarded as the highest honor in the field of mineral engineering. I am deeply moved by this tribute, which suggests not only regard for my service to the profession but also the affectionate esteem of my fellow mineral engineers. You have made me happy at the prospect of the permanent association of my name with that of Robert Hallowell Richards and of the distinguished recipients of the award, Arthur Fay Taggart, Frank R. Milliken, John F. Myers, Edward William Englemann, C. Harry Benedict, Edward W. Davis and Arthur W. Fahrenwald. I wish to thank you all for an honor so generously bestowed. Professor Richards is known to us all as a legendary figure, and we can read about him in the Richards Memorial Volume of our Transactions. Some of us have even had the good fortune of knowing him. I count myself among those lucky few. In its intangible attributes the Award recalls those things for which Professor Richards stood: for Science in Art, for thoroughness, for meticulous accuracy, for bold imaginativeness, most of all for professional integrity. Now, as in his day, these attributes are central to an engineer's creed. They are appropriately needed in a formulation of a definition of the mineral engineering profession.

Jan 6, 1957

Jan 1, 1967

By G. W. King, A. Bogrow, L. F. Marek

The purpose of this paper is to present the data and some interpretation of the results of a laboratory study of the reduction of iron ore and the deposition of carbon from the reducing gas mixtures in such reductions. One major object of the study was to determine the effect of gas pressures on these chemical processes. Effort was made to approximate the conditions of temperature, gas composition, linear and mass gas velocities, pressure range, and extent of reduction prevailing in commercial blast furnaces. The results show that the reduction of Fe203 proceeds by two steps, largely consecutive under the conditions used herein: reduction of Fe203 to FeO, and reduction of FeO to Fe. Unless the gas has a CO!CO, ratio greater than 2.1 only the first step occurs under these conditions (850°C) but the following generalizations apply to either step or to the combination. The rate of reduction of relatively fine ore particles .at any time is proportional to the mass rate of supply of CO (provided some of it is thermodynamically available): the rate therefore is proportional to the linear velocity at constant pressure, or to the pressure at constant linear velocity. Thus, the rate of reduction may be increased without increase in linear velocity of the reducing gas by increasing the mass velocity of the gas and increasing the pressure correspondingly to avoid any increase in the linear velocity. The rate "constants"—i.e., the efficiency of conversion of the "available" CO supplied— is not actually constant but decreases as the reduction proceeds, and is a function only of the state of the ore; i.e., of the amount of reduction already accomplished and hence of the amount of CO passed. The particle size of ore used in nearly all the experiments was relatively small (8 to 14-mesh). The rate of reduction in run 16 with 3 to 8-mesh ore particles is within experimental error the same as with the finer ore. Although this would indicate an absence of effect due to particle size in this range of ore particles, it is desirable to have more data on other ore sizes and on ore of different densities before arriving at any generalizations on this point. Although it is possible to extend the analysis of these results to consideration of the more detailed kinetics and mechanism of iron oxide reduction, such extension is beyond the scope of the present paper. From the experiments on carbon deposition, it was evident that if carbon deposition is increased at all by the application of pressures up to 10 psi ga., such increase appears to be less than the experimental and analytical error. It appears safe to conclude that at top pressures on the order

Jan 1, 1948

By L. F. Marek, G. W. King, A. Bogrow

The purpose of this paper is to present the data and some interpretation of the results of a laboratory study of the reduction of iron ore and the deposition of carbon from the reducing gas mixtures in such reductions. One major object of the study was to determine the effect of gas pressures on these chemical processes. Effort was made to approximate the conditions of temperature, gas composition, linear and mass gas velocities, pressure range, and extent of reduction prevailing in commercial blast furnaces. The results show that the reduction of Fe203 proceeds by two steps, largely consecutive under the conditions used herein: reduction of Fe203 to FeO, and reduction of FeO to Fe. Unless the gas has a CO!CO, ratio greater than 2.1 only the first step occurs under these conditions (850°C) but the following generalizations apply to either step or to the combination. The rate of reduction of relatively fine ore particles .at any time is proportional to the mass rate of supply of CO (provided some of it is thermodynamically available): the rate therefore is proportional to the linear velocity at constant pressure, or to the pressure at constant linear velocity. Thus, the rate of reduction may be increased without increase in linear velocity of the reducing gas by increasing the mass velocity of the gas and increasing the pressure correspondingly to avoid any increase in the linear velocity. The rate "constants"—i.e., the efficiency of conversion of the "available" CO supplied— is not actually constant but decreases as the reduction proceeds, and is a function only of the state of the ore; i.e., of the amount of reduction already accomplished and hence of the amount of CO passed. The particle size of ore used in nearly all the experiments was relatively small (8 to 14-mesh). The rate of reduction in run 16 with 3 to 8-mesh ore particles is within experimental error the same as with the finer ore. Although this would indicate an absence of effect due to particle size in this range of ore particles, it is desirable to have more data on other ore sizes and on ore of different densities before arriving at any generalizations on this point. Although it is possible to extend the analysis of these results to consideration of the more detailed kinetics and mechanism of iron oxide reduction, such extension is beyond the scope of the present paper. From the experiments on carbon deposition, it was evident that if carbon deposition is increased at all by the application of pressures up to 10 psi ga., such increase appears to be less than the experimental and analytical error. It appears safe to conclude that at top pressures on the order

Jan 1, 1948

By J. M. Silliman

Several years ago, having occasion to determine the amount of some very slight atmospheric depressions, I devised and had constructed by a skilful tinsmith the manometer shown in the accompanying drawing. It consists of a cylindrical vessel of tin, 6.6 inches in diameter, through the sides of which, at a distance of about six inches from the top, passes an air-tube D, its upper extremity terminating 3.5 inches from the top. Within the vessel is a combined cylipdrical

Jan 1, 1889

Edwin A. SpeRry, Denver, Colo. (communication to the Secretary*) :—Since writing my former paper on this subject I have had several discussions concerning some of the statements contained therein, with men who have had a large experience with the old form of buddle, both in this country and in Cornwall. The present paper gives a brief statement of some of the points debated, together with the arguments and proofs in their substantiation. The first point is the question of the capacity. In my origi-

Jan 1, 1904

By A. G. Allten

EXAMINATION by metallographic and X-ray diffraction means of an austenitic steel containing 0.06 pct C, 1.26 pct Mn, 0.38 pct Si, 21.15 pct Ni, 18.72 pct Cr, 3.07 pet W, and 9.14 pet Mo indicated that a - phase, which had not been reported in the literature, existed in this steel. Both the s and car-bides of the M6 C type were present in the as-forged steel. The carbides dissolved completely in the aus-tenite at approximately 2200°F (1205°C). The s, however, was present at all temperatures up to the solidus temperature of the steel at approximately 2375°F (1300°C). Ferrite was not found in any condition of the steel. The faintness of some of the s lines in X-ray patterns obtained from samples of the steel made it desirable to isolate the s prior to verification of its entire pattern. It was found that the s phase could be separated from samples of the steel which had been water quenched from 2250°F (1230°C) by dis-

Jan 1, 1955

By William E. Ford, Edward Salisbury Dana

URANINITE. Cleveite. Broggerite. Nivenite. Pitchblende. Isometric. In octahedrons (o), also with dodecahedra1 faces (d) ; less often in cubes with o and d. Crystals rare. Usually massive and botryoidal; also in grains; structure sometimes columnar, or curved lamellar. Fracture conchoidal to uneven. Brittle. H. = 5'5. G. = 9'0 to 9'7 of crystals; of massive altered forms from 6'4 upwards. Luster submetallic, to greasy or pitch-like, and dull. Color grayish, greenish, brownish, velvet- black. Streak brownish black, grayish, olive-green, a little shining. Opaque. Comp. -A uranate of uranyl, lead, usually thorium (or zirconium), often the metals of the lanthanum and yttrium groups; also containing the gases nitrogen, helium and argon, in varying amounts up to 2'6 p. c. Calcium and water (essential?) are present in small quantities; iron also, but only as an impurity. The relation between the bases varies widely and no definite for- mula can be given. Radium was first discovered in this mineral and it has been shown that it and the helium present are products of the breaking down of the uranium.

Jan 1, 1922

By W. B. Morrison

Anderson, King, and Spreadborough present detailed evidence to show what ~aldwin~' has already pointed out, that, over a relatively small grain-size range (Ad"1/2 ^ 10 mm-'I2, d is average grain diameter), yield point data can fit a number of relationships. Part of the difficulty in obtaining data which reflect only the effect of change in grain size on yielding arises from the fact that in varying the grain size, even though great care is taken, other structural changes are almost certain to occur. In iron alloys, these changes may consist of variations in subgrain size, grain boundary ledge density, and degree of carbon and nitrogen segregation at grain boundaries, all of which are difficult to detect and which may affect yielding, primarily through their effect on dislocation generation. Because of the inherent inaccuracy associated with yield point measurements there is little point in using relatively complex equations to fit data, as was done by Anderson et mnl., rather than the simpler, widely used Hall-Petch equation. In compiling their table of data, it is surprising that they did not include results from certain low-carbon steels,31 in which, as illustrated in Fig. 2, the grain-size range is very much larger than in their Armco Iron. The very fine grains in these steels were obtained by a thermomechanical process. Examination by electron microscopy showed that the grains were separated by high-angle boundarie and contained only an occasional subboundary. The data from these steels obeyed the Hall-Petch equation, and it was shown quite conclusively that they did not fit a d-l or (1-lJ3 relationship. Obviously, a much wider range in grain size than used by Anderson et al. is desirable if we are to determine the true relation between lower yield stress and grain size.

Jan 1, 1969

By E. H. Erwin Gartner

The Rhenish lignite deposit in the Nordrhein-Westphalia province of the German Federal Republic covers an area on the left bank of the Rhine River of about 970 sq miles (Fig. 1). Here, in the Miocene era, some 20 million years ago a lignite seam was formed and later broken, through tectonic movements into several blocks, some thrown down into depths of over 1,500 ft. This deposit consists of a single seam, in places up to 300 ft thick, but averaging about 150 ft. In a few areas, it is split into as many as five seams, separated by barren strata. It contains about 60 billion tons (2000 lb/short ton) of lignite which, however, being relatively young geologically, has, because of approximately 60% moisture, 2 to 8% ash, and low sulfur, a net calorific value of 3,340 Btu. That calorific value increases, however, with rising thickness of the cap rock. About one-third of the yearly production of 90 to 100 million tons of raw lignites is converted into briquets. Raw lignite is pulverized and dried to about 18% water content and then pressed without binder into briquets under a pressure of about 14,000 psi. The briquets are being used primarily for residential heating; their sales, however, have been declining sharply since 1963. On the other hand, the volume of raw lignite used in steam power plants has been rising steadily and amounts at present (1968) to about two-thirds of the total production. Huge steam power plants, such as Frimmersdorf, shown in Fig. 2 (which, with an installed capacity of 2,600 MW [megawatt], represents the world's largest steam power plant) with a generating capacity of up to 300 MW per unit and a total installed capacity of over 6,000 MW, contribute about 26% of the total electric power production of the German Federal Republic.

Jan 1, 1969

By T. Sterry Hunt

THERE are about sixty bodies which chemists call elements ; the simplest forms of matter which they have been able to extract from the rocky crust of our earth, its waters, and its atmosphere. These substances are distributed in very unequal quantities, and in very different manners. As regards the frequency of these elements in nature, neglecting for the present those which constitute air and water, and confining ourselves to the solid matters of the earth's crust, there are a few which are exceedingly abundant, making up nine-tenths, if not ninety-five hundredths, of the rocks so far as known to us. The elements of which silica, alumina, lime, magnesia, potash, and soda are oxides, are very common, and occur almost everywhere. There are others which are much rarer, being found in comparatively small quantities. Many of these rarer elements are, however, of great importance in the economy of nature. Such are the common metals and other substances used in the arts, which occur in nature in quantities relatively very minute, but which have been collected by various agencies, and thus made available for the wants of man. It is chiefly of the well-known metals, iron, copper, silver, and gold, that I propose to speak to-night ; but there are two other elements not classed among the metals, which I shall notice for the reason that their history is extremely important, and will, moreover, enable , us to comprehend more clearly some points in that of the metals themselves. I speak of phosphorus and iodine. You all know the essential part which the former of these, com-

Jan 1, 1968

By R. H. Harrington

The definition of precipitation-hardening1 is well understood and its principles have been subjected to study for some time. However, the variation of properties with double aging, combined with strain-hardening, gives promise of new and useful phenomena. Properly to understand these distinctions, definitions of these terms are necessary. Precipitation-hardening1.—This reaction usually depends upon an alloy having such a composition that it consists only, or in major part, of but one phase, a solid solution, at a high temperature, so that, upon slow cooling, this solution breaks down into two phases, the solid solution and a compound. By heating the alloy to the temperature for maximum solution of the compound, quenching, and reheating to a suitable lower temperature for critical dispersion precipitation of the compound, useful properties of the alloy may be developed to a maximum. Double Aging.—Dougle aging in part is similar to the process for precipitation-hardening, consisting of heating a precipitation-hardening alloy to the solution temperature, quenching, reheating to the suitable dispersion precipitation temperature, strain-hardening, and again reheating to a suitable temperature to develop certain useful properties to a maximum. The strain-hardening may be induced by two methods: (I) a rate of cooling from the first reheat may suffice to strain the solid solution lattice of the alloy; or (2) the alloy may be cold-worked to a suitable degree between the two reheats. Pkecipitation-hardening of Copper-cobalt-beryllium Alloys1.2 The composition of principal interest is that of 2.6 per cent Co, 0.4 per cent Be, 97 per cent Cu. The alloy has been developed commercially and, with certain reasonable precautions, ordinary brass-foundry practice suffices to produce an alloy of high quality. Preliminary Precipitation-hardening Study.—Samples were cut from a I-in. round rod cast in a graphite mold. These samples were then

Jan 1, 1937

By G. R. Speich

The age-hardening of Fe-18 to 21 pct Ni marten-sites containing small amounts of titanium, aluminum, copper, or molybdenum has been studied by hardness measurements, transmission electron microscopy, extraction replicas, and X-ray and electron diffraction. Electyon-probe microanaly-sis of the extracted precipitates was also performed. The effects of temperature and composition on the aging kinetics have been studied in detail for Fe-20 pctNi-Ti martensites. All the martensites hardened on aging at 400" to 500 "C with a single aging peak. In the Fe-20 pct Ni-Ti martensites hardening was associated with the formation of a fine dispersion of NisTi. No precipitation was observed in an Fe-21 pct Ni-2.6 pct A1 alloy, although the hardness increased from 327 to 545 Dph during aging at 500°C. Copper was precgitated from an Fe-20 pct Ni-10.7pct Cu alloy, at least during the later stages of age-hardening. Hardening in an Fe-18 pctNi-5pct Mo alloy was associated with the precipitation of an intemzetallic compound tentatively identified as NisMo. The formation of austenite and the recovery of the defect structure of the martensite occur simultaneously with the normal precipitation processes &ring aging of these alloys. THE age-hardening of substitutional iron-base martensites is an important subject for study since age-hardening is one of the principal means of strengthening the substitutional iron-base martensites in precipitation-hardening stainless steels1 and maraging steels.a~4 In contrast to Fe-C martensites, these martensites are relatively soft and ductile in the as-quenched condition, due to the low solid-solution hardening effect of the substitutional elements as compared to carbon. Also, these martensites are hardened by aging at low temperatures in contrast to Fe-C martensites which generally soften on tempering. Titanium and aluminum, singly or in combination, as well as copper and molybdenum, have been the principal alloying additions to stainless steels to obtain an age-hardening reaction.' Ti-A1 or Co-Mo-Ti combinations have been used in the case of maraging steels.3"4 The present work has been confined to a study of the age-hardening characteristics of an Fe-18 to 21 pct Ni martensite to which small amounts of titanium, aluminum, copper, and molybdenum were added in order to study the effects of each alloying element separately. The age-hardening characteristics of these alloys were studied by hardness measurements, transmission electron microscopy, extraction replicas, and X-ray and electron diffraction. Electron-probe micro-analysis of the extracted precipitates was also performed. The types and dispersion of precipitates, the formation of austenite, and the recovery of the defect structure of the martensite all were studied. EXPERIMENTAL PROCEDURE Alloys. The compositions of the alloys studied are listed in Table I. The level of 18 to 21 pct Ni was chosen to assure complete transformation to martensite on quenching and is the same nickel level used in maraging steels. The concentrations of titanium, aluminum, copper, and molybdenum were chosen after a study of the and Fe-Ni-MO' ternary diagrams indicated how much of each alloying element could be dissolved in austenite. Alloys with 2 and 4 pct Cu were also studied, but these did not show precipitation hardening at the nickel levels studied and will not be discussed further. The alloys were prepared from electrolytic iron and high-purity* nickel, titanium, aluminum, copper, and molybdenum by vacuum melting of 20-lb heats. These were vacuum-cast into two 8-lb ingots. The ingots were hot-rolled at 1100°C to 1/2-in. plate and subsequently cut into 3/8-in. cubes. The cubes were sealed in evacuated quartz capsules and solution-treated for 16 hr at 1100°C, except for the Fe-20 pct Ni-10.7 pct Cu alloy and Fe-21 pct Ni-2.6 pct A1 alloys which were solution-treated for 16 hr at 1300" and at 1250"C, respectively. Metallographic examina-

Jan 1, 1963